Solid catalyst component and catalyst for olefins polymerization

ABSTRACT

Solid catalyst components and catalysts which contain (a) magnesium compound, (b) titanium tetrachloride, and (c) a phthalic acid diester or its derivative are useful in the synthesis of olefin polymers in high yields. Particularly, propylene polymers can be obtain in very high yields while retaining high stereoregularity.

TECHNICAL FIELD

The present invention relates to a solid catalyst component and catalystfor polymerization of olefins, which have a high responsiveness tohydrogen and can afford olefin polymers in very high yield whileretaining high stereoregularity.

BACKGROUND ART

So far it has been known that some solid catalyst components used inpolymerization of olefins contain magnesium, titanium, an electron donorcompound and halogen as essential components. A large number of methodsfor olefin polymerization by polymerization or copolymerization ofpropylene, in the presence of a catalyst for olefin polymerizationcomprising the above solid catalyst components, an organoaluminumcompound and organosilicon compound, have been proposed. For example,Japanese Unexamined Patent Publication No. (herein after referred to asJP-A) 57-63310/1982 and JP-A 57-63311/1982 disclose a method forpolymerization of olefins of 3 carbon atoms or more, in which a combinedcatalyst comprising solid catalyst components containing a magnesiumcompound, titanium compound and an electron donor such as diestercompound, e.g., phthalic acid ester, and an organoaluminum compound andan organosilicon compound having a Si—O—C linkage is used.

JP-A 1-6006/1989 discloses solid catalyst components for olefinpolymerization, which contain a dialkoxymagnesium, titaniumtetrachloride, and dibutyl phthalate, wherein propylene is somewhateffectively polymerized in the presence of the solid catalyst componentsto give a stereoregular polymer in high yield. In this situation, thepolymers produced with the above catalysts have been utilized in variousways as molding products such as cars and household electric appliancesas well as containers and films. In producing these products, polymerpowder is melted and molded in anyone of various forming machines.Particularly, in producing large-sized molding products by means ofinjection molding, high fluidity (melt flow rate) of melted polymers issometimes required, and many researches have been continued accordinglyin order to enhance the melt flow rate of polymers.

The melt flow rate greatly depends on the molecular weight of polymers.In the polymer trade, it is general to add hydrogen as a molecularweight regulator for the polymer produced in polymerization of olefins.When low molecular weight polymers are produced, i.e., in order toproduce polymers of high melt flow rate, a large quantity of hydrogen isusually added, though there is a limitation in a pressure reactor interms of safety as well as in an adaptable amount of hydrogen. In orderto add a much more amount of hydrogen, the partial pressure of monomerto be polymerized has to be decreased, but decrease of the partialpressure is accompanied by decrease of productivity. Additionally, useof a large amount of hydrogen may bring about a problem of cost. It hasbeen desired, accordingly, that a catalyst capable of producing polymersof high melt flow rate with a lesser amount of hydrogen could bedeveloped. In other words, a catalyst which has a high activity tohydrogen or high responsiveness to hydrogen and which gives a highlystereoregular polymer in high yield is expected to be developed. In theabove-mentioned prior art, however, it is not sufficient to solve such aproblem.

That is, the purpose of the present invention is to solve such a problemremaining in the prior art and to provide a solid catalyst component andcatalyst for polymerization of olefins, which can afford olefin polymersin very high yield, in particular, which can afford propylene polymersin very high yield while retaining high stereoregularity, and which havea high responsiveness to hydrogen.

DISCLOSURE OF INVENTION

The present inventors worked assiduously to solve the problems remainingin the above-mentioned prior art and found that a solid catalystcomponent comprising a magnesium compound, titanium tetrachloride, and aparticular phthalic acid diester or a derivative thereof exhibit veryhigh activity in polymerization of olefins, particularly inpolymerization of propylene to give propylene polymers in high yieldwith retaining a high stereoregularity, and moreover the components havehigh competence to hydrogen. Thus, the invention was completed.

That is, the solid catalyst component (hereinafter sometimes referred toas “component (A)”) for polymerization of olefins to attain theabove-mentioned purpose according to the present invention arecharacterized in that they comprise (a) a magnesium compound, (b)titanium tetrachloride, and (c) a phthalic acid diester or a derivativethereof of the following general formula (1):

(wherein R¹ is an alkyl group of 1 to 8 carbon atoms or halogen atom; R²and R³ are the same or different, representing an alkyl group of 1 to 12carbon atoms; the number n of the substituent R¹ is 0, 1 or 2, and whenn is 2, R¹ may be the same or different; provided that when n is 0, R²and R³ each is an alkyl group of 4 to 8 carbon atoms having a tertiarycarbon atom).

Moreover, the catalysts for polymerization of olefins in the presentinvention comprise:

(A) the above-mentioned solid catalyst components for polymerization ofolefins;

(B) an organoaluminum compound of the following general formula (2):

R⁴ _(p)AlQ_(3−p)  (2)

(wherein R⁴ is an alkyl group of 1 to 4 carbon atoms; Q is hydrogen atomor halogen atom; and p is an integer of 0<p≦3); and

(C) an organosilicon compound of the following general formula (3):

R⁵ _(q)Si(OR⁶)_(4−q)  (3)

(wherein R⁵ is the same or different, representing an alkyl group of 1to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group,an allyl group, or an aralkyl group; R⁶ is the same or different,representing an alkyl group of 1 to 4 carbon atoms, a cycloalkyl group,a phenyl group, a vinyl group, an allyl group, or an aralkyl group; q isan integer of 0≦q≦3).

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a flowchart illustrating a process for preparing the catalystfor polymerization in the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

The magnesium compound used in preparation of the component (A) in thepresent invention (hereinafter sometimes referred to as “component (a)”)include magnesium dihalide, dialkyl magnesium, alkylmagnesium halide,dialkoxymagnesium, diaryloxymagnesium, alkoxymagnesium halide, fattyacid magnesium, and the like.

Specific examples of the magnesium dihalide include magnesiumdichloride,magnesiumdibromide, magnesiumdiiodide, magnesium difluoride, and thelike. The dialkylmagnesium may preferably be represented by the generalformula R⁷R⁸Mg (wherein R⁷ and R⁸ are the same or different,representing an alkyl group of 1 to 10 carbon atoms), more specificallyincluding dimethylmagnesium, diethylmagnesium, methylethylmagnesium,dipropylmagnesium, methylpropylmagnesium, ethylpropyl magnesium,dibutylmagnesium, methylbutylmagnesium, ethylbutylmagnesium, and thelike. The dialkylmagnesium may be prepared by reacting metal magnesiumwith a hydrocarbon halide or alcohol.

The alkylmagnesium halide is preferably represented by the generalformula R⁹MgD₁ (wherein R⁹ is an alkyl group of 1 to 10 carbon atoms;and D¹ is a halogen atom such as chlorine atom, bromine atom, iodineatom, or fluorine atom), more specifically including ethyl-magnesiumchloride, propylmagnesium chloride, butylmagnesium chloride, and thelike. The magnesium halide may be prepared by reacting metal magnesiumwith a hydrocarbon halide or alcohol.

The dialkoxymagnesium or diaryloxymagnesium is preferably represented bythe general formula Mg(OR¹⁰)(OR¹¹)(wherein R¹⁰ and R¹¹ are the same ordifferent, representing an alkyl group of 1 to 10 carbon atoms or arylgroup), more specifically including dimethoxymagnesium,diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium,diphenoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxy magnesium,butoxyethoxymagnesium, and the like. The dialkoxymagnesium ordiaryloxymagnesium may be prepared by reacting metal magnesium with analcohol in the presence of a halogen or halogen-containing metalcompound.

The alkoxymagnesium halide is preferably represented by the generalformula Mg(OR¹²)D² (wherein R¹² is an alkyl group of 1 to 10 carbonatoms; D² is a halogen atom such as chlorine atom, bromine atom, iodineatom, or fluorine atom), more specifically including methoxy-magnesiumchloride, ethoxymagnesium chloride, propoxymagnesium chloride,butoxymagnesium chloride, and the like.

The fatty acid magnesium is preferably represented by the generalformula Mg(R¹³COO)₂ (wherein R¹³ is an alkyl group of 1 to 20 carbonatoms), more specifically including magnesium laurate, magnesiumstearate, magnesium octanoate, magnesium decanoate, and the like.

Among these magnesium compounds in the present invention, thedialkoxymagnesium is preferred, particularly diethoxymagnesium anddipropoxymagnesium are preferably used. The above-mentioned magnesiumcompounds may be used alone or in a combination of two or more.

When the dialkoxymagnesium is used as the component (a) in theinvention, the alkoxymagnesium is in a form of granules or powder, whichmay also be used in an amorphous or spherical shape. For example, whenthe dialkoxymagnesium is used in a spherical shape, it is possible toobtain polymer powder which has a better granular form and narrowerparticle size distribution. Thus, handling and operability of theproduced polymer powder during polymerization procedure are improved,and such a problem as obstruction, etc., caused by fine powder containedin the produced polymer powder can be solved.

The above-mentioned dialkoxymagnesium in a spherical shape needn'tnecessarily be completely round, and may be used in an ellipsoidal orpebble-like. Specifically, the ratio (l/w) of the longitudinal axis (l)to the minor axis (w) is usually 3 or less, preferably from 1 to 2, morepreferably from 1 to 1.5, in the granular shape. Methods for producingsuch a spherical dialkoxymagnesium are described in, for example, JP-A58-41832/1983, JP-A 62-51633/1987, JP-A 3-74341/1991, JP-A4-368391/1992, and JP-A 8-73388/1996.

The mean particle size of the above-mentioned dialkoxymagnesium isusually from 1 to 200 μm, preferably from 5 to 150 μm. In the sphericaldialkoxymagnesium, the mean particle size is usually from 1 to 100 μm,preferably from 5 to 50 μm, more preferably from 10 to 40 μm. As forparticle size, it is desirable to use those in which the content of fineand coarse powder is small and the particle size distribution islimited. Specifically, the content of the granule of 5 μm or less is 20%or less, preferably 10% or less. On the other hand, that of 100 μm ormore is 10% or less, preferably 5% or less. Moreover, the particle sizedistribution represented by ln(D90/D10)(wherein D90 means particle sizeat 90% of integrated particle size, and D10 means particle size at 10%of integrated particle size) is 3 or less, preferably 2 or less.

In the present invention, though titanium tetrachloride (hereinaftersometimes referred to as “component (b)”) is used in preparation of thecomponent (A), other type of titanium halides than titaniumtetrachloride may also be used with titanium tetrachloride. The titaniumhalide is exemplified by an alkoxytitanium chloride of the generalformula Ti(OR¹⁴)_(n)Cl_(4−n) (wherein R¹⁴ is an alkyl group of 1 to 4carbon atoms; and n is an integer of 1≦n≦3). The above-mentionedtitanium halide may be used alone or in a combination of two or more.Specifically, Ti(OCH₃)Cl₃, Ti(OC₂H₅)Cl₃, Ti(OC₃H₇)Cl₃, Ti(O-n-C₄H₉)Cl₃,Ti(OCH₃)₂Cl₂, Ti(OC₂H₅)₂Cl₂, Ti(OC₃H₇)₂Cl₂₆₃₈ ₆, Ti(O-n-C₄H₉)₂Cl₂,Ti(OCH₃)₃Cl, Ti(OC₂H₅)₃Cl, Ti(OC₃H₇)₃Cl, Ti(O-n-C₄H₉)₃Cl, and the likeare exemplified.

As for the phthalic acid diesters or their derivatives (hereinaftersometimes referred to as “component (c)”) used in preparation of thecomponent (A) in the present invention, R¹ in the above-mentionedgeneral formula (1) includes alkyl groups of 1 to 8 carbon atoms,specifically including methyl group, ethyl group, n-propyl group,isopropyl group, n-butyl group, isobutyl group, tert-butyl group,n-pentyl group, isopentyl group, neopentyl group, n-hexyl group,isohexyl group, 2,2-dimethylbutyl group, 2,2-dimethylpentyl group,isooctyl group, 2,2-dimethylhexyl group, and the like, and halogen atomsuch as fluorine atom, chlorine atom, bromine atom, and iodine atom;preferably, methyl group, ethyl group, tert-butyl group, chlorine atom,bromine atom or fluorine atom is exemplified, and more preferably,methyl group, tert-butyl group, chlorine atom, bromine atom or fluorineatom is exemplified.

In R² and R³ of the above-mentioned general formula (1), the alkyl groupof 1 to 8 carbon atoms includes the same groups as those of R¹ asmentioned above; and the alkyl group of 9 to 12 carbon atoms includesn-nonyl group, isononyl group, n-decyl group, isodecyl group, andn-dodecyl group. Among these groups, preferred are ethyl group, n-butylgroup, isobutyl group, tert-butyl group, neopentyl group, isohexylgroup, and iso-octyl group, and particularly preferred are ethyl group,n-butyl group, neopentyl group, and isohexyl group.

When the number n of the substituent R¹ is 1, R¹ is substituted for thehydrogen atom at the 3, 4 or 5 position of the phthalic acid derivativeof the above general formula (1). When n is 2, R¹ is substituted for thehydrogen atoms at the 4 and 5 positions. However, the substituent R¹ ispreferably substituted at least for the hydrogen atom at the 4 or 5position of the benzene ring.

In the present invention, the phthalic acid diesters and theirderivatives represented by the above-mentioned general formula (1), whenn is 0 and R² and R³ each is an alkyl group of 4 to 8 carbon atomshaving a tertiary carbon atom, specifically include ethyl neopentylphthalate, butyl neopenthyl phthalate, tert-butyl neopentyl phthalate,isohexyl neopentyl phthalate, dineopentyl phthalate, isooctyl neopentylphthalate, and the like. In the above general formula (1), when n is 1or 2, R¹ is an alkyl group of 1 to 5 carbon atoms or halogen atom, andR² and R³ each is an alkyl group of 4 to 8 carbon atoms having atertiary carbon atom, they include dineopentyl 3-methylphthalate,dineopentyl 4-methylphthalate, dineopentyl 3-ethylphthalate, dineopentyl4-ethylphthalate, tert-butyl neopentyl 3-methylphthalate, tert-butylneopentyl 4-methylphthalate, tert-butyl neopentyl 3-ethylphthalate,tert-butyl neopentyl 4-ethylphthalate, dineopentyl4,5-dimethylphthalate, dineopentyl 4,5-diethyl-phthalate, tert-butylneopentyl 4,5-dimethylphthalate, tert-butyl neopentyl4,5-diethylphthalate, dineopentyl 3-fluorophthalate, dineopentyl3-chlorophthalate, dineopentyl 4-chlorophthalate, dineopentyl4-bromophthalate, and dineopentyl 4-tert-butylphthalate. Among thesecompounds, preferred are dineopentyl phthalate, dineopentyl4-methylphthalate, dineopentyl 4,5-dimethylphthalate, dineopentyl4-ethylphthalate, dineopentyl 4,5-diethyl-phthalate, dineopentyl4-bromophthalate, dineopentyl 4-tert-butylphthalate, tert-butylneopentyl phthalate, and dineopentyl 3-fluorophthalate.

In the above general formula, where n is 2, one of R¹ is a halogen atomand the other is an alkyl of 1 to 8 carbon atoms, and at least one of R²and R³ is an alkyl of 1 to 12 carbon atoms other than the alkyl groupsof 4 to 8 carbon atoms having a tertiary carbon atom, they includediethyl 4-methyl-5-chlorophthalate, diethyl 4-methyl-5-bromophthalate,diethyl 4-ethyl-5-chlorophthalate, diethyl 4-ethyl-5-bromophthalatedi-n-butyl 4-methyl-5-chlorophthalate, di-n-butyl4-methyl-5-bromophthalate, di-n-butyl 4-ethyl-5-chlorophthalate,di-n-butyl 4-ethyl-5-bromophthalate, diisobutyl4-methyl-5-chloro-phthalate, diisobutyl 4-methyl-5-bromophthalate,diisobutyl 4-ethyl-5-chlorophthalate, diisobutyl4-ethyl-5-bromo-phthalate, diisohexyl 4-methyl-5-chlorophthalate,diisohexyl 4-methyl-5-bromophthalate, diisohexyl4-ethyl-5-chloro-phthalate, diisohexyl 4-ethyl-5-bromophthalate,diisooctyl 4-methyl-5-chlorophthalate, diisooctyl4-methyl-5-bromo-phthalate, diisooctyl 4-ethyl-5-chlorophthalate,diisooctyl 4-ethyl-5-bromophthalate, ethyl-n-butyl4-methyl-5-chloro-phthalate, ethyl-n-butyl 4-chloro-5-methylphthalate,ethyl-n-butyl 4-methyl-5-bromophthalate, ethyl-n-butyl4-bromo-5-methylphthalate, ethyl-n-butyl 4-ethyl-5-chloro-phthalate,ethyl-n-butyl 4-chloro-5-ethylphthalate, ethyl-n-butyl4-ethyl-5-bromophthalate, ethyl-n-butyl 4-bromo-5-ethyl-phthalate, ethylisobutyl 4-methyl-5-chlorophthalate, ethyl isobutyl4-chloro-5-methylphthalate, ethyl isobutyl 4-methyl-5-bromophthalate,ethyl isobutyl 4-bromo-5-methyl-phthalate, ethyl isobutyl4-ethyl-5-chlorophthalate, ethyl isobutyl 4-chloro-5-ethylphthalate,ethyl isobutyl 4-ethyl-5-bromophtalate, ethyl isobutyl4-bromo-5-ethyl-phthalate, ethyl isohexyl 4-methyl-5-chlorophthalate,ethyl isohexyl 4-chloro-5-methylphthalate, ethyl isohexyl4-methyl-5-bromo phthalate, ethyl isohexyl 4-bromo-5-methyl-phthalate,ethyl isohexyl 4-ethyl-5-chlorophthalate, ethyl isohexyl4-chloro-5-ethylphthalate, ethyl isohexyl 4-ethyl-5-bromo phthalate,ethyl isohexyl 4-bromo-5-ethylphthalate, n-butyl isobutyl4-methyl-5-chlorophthalate, n-butyl isobutyl 4-chloro-5-methylphthalate,n-butyl isobutyl 4-methyl-5-bromophthalate, n-butyl isobutyl4-bromo-5-methyl phthalate, n-butyl isobutyl 4-ethyl-5-chlorophthalate,n-butyl isobutyl 4-chloro-5-ethylphthalate, n-butyl isobutyl4-ethyl-5-bromophthalate, n-butyl isobutyl 4-bromo-5-ethyl phthalate,n-butyl isohexyl 4-methyl-5-chlorophthalate, n-butyl isohexyl4-chloro-5-methylphthalate, n-butyl isohexyl 4-methyl-5-bromophthalate,n-butyl isohexyl 4-bromo-5-methylphthalate, n-butyl isohexyl4-ethyl-5-chlorophthalate, n-butyl isohexyl 4-chloro-5-ethylphthalate,n-butyl isohexyl 4-ethyl-5-bromophthalate, and n-butyl isohexyl4-bromo-5-ethylphthalate. In the above general formula, where n is 1 or2, R¹ is an alkyl group of 1 to 8 carbon atoms, and R² and R³ each is analkyl of 1 to 12 carbon atoms other than the alkyl groups of 4 to 8carbon atoms both having a tertiary carbon atom, they include diethyl3-methylphthalate, diethyl 4-methylphthalate, diethyl 3-ethylphthalate,diethyl 4-ethylphthalate, diethyl 3-tert-butylphthalate, diethyl4-tert-butylphthalate, diethyl 3-n-butylphthalate, diethyl4-n-butylphthalate, diethyl 4,5-dimethylphthalate, diethyl4,5-diethylphthalate, diethyl 4-methyl-5-ethylphthalate, diethyl4-methyl-5-tert-butyl-phthalate, diethyl 4-ethyl-5-tert-butylphthalate,di-n-butyl 3-methylphthalate, di-n-butyl 4-methylphthalate, di-n-butyl3-ethylphthalate, di-n-butyl 4-ethylphthalate, di-n-butyl3-tert-butylphthalate, di-n-butyl 4-tert-butylphthalate, di-n-butyl3-n-butylphthalate, di-n-butyl 4-n-butylphthalate, di-n-butyl4,5-dimethylphthalate, di-n-butyl 4,5-diethylphthalate, di-n-butyl4-methyl-5-ethylphthalate, di-n-butyl 4-methyl-5-tert-butylphthalate,di-n-butyl 4-ethyl-5-tert-butylphthalate, diisobutyl 3-methylphthalate,diisobutyl 4-methylphthalate, diisobutyl 3-ethylphthalate, diisobutyl4-ethylphthalate, diisobutyl 3-tert-butylphthalate, diisobutyl4-tert-butylphthalate, diisobutyl 3-n-butylphthalate, diisobutyl4-n-butylphthalate, diisobutyl 4,5-dimethyl-phthalate, diisobutyl4,5-diethylphthalate, diisobutyl 4-methyl-5-ethylphthalate, diisobutyl4-methyl-5-tert-butyl-phthalate, diisobutyl4-ethyl-5-tert-butylphthalate, diisohexyl 3-methylphthalate, diisohexyl4-methylphthalate, diisohexyl 3-ethylphthalate, diisohexyl4-ethylphthalate, diisohexyl 3-tert-butylphthalate, diisohexyl4-tert-butyl-phthalate, diisohexyl 3-n-butylphthalate, diisohexyl4-n-butylphthalate, diisohexyl 4,5-dimethylphthalate, diisohexyl4,5-diethylphthalate, diisohexyl 4-methyl-5-ethylphthalate, diisohexyl4-methyl-5-tert-butylphthalate, diisohexyl4-ethyl-5-tert-butylphthalate, diisooctyl 3-methylphthalate, diisooctyl4-methylphthalate, diisooctyl 3-ethylphthalate, diisooctyl4-ethylphthalate, diisooctyl 3-tert-butyl-phthalate, diisooctyl4-tert-butylphthalate, diisooctyl 3-n-butylphthalate, diisooctyl4-n-butylphthalate, diisooctyl 4,5-dimethylphthalate, diisooctyl4,5-diethylphthalate, diisooctyl 4-methyl-5-ethylphthalate, diisooctyl4-methyl-5-tert-butylphthalate, diisooctyl4-ethyl-5-tert-butyl-phthalate, di-n-decyl 4-methylphthalate, diisodecyl4-methylphthalate, di-n-decyl 4-ethylphthalate, diisodecyl4-ethylphthalate, ethyl n-butyl 3-methylphthalate, ethyl n-butyl4-methylphthalate, ethyl n-butyl 3-ethylphthalate, ethyl n-butyl4-ethylphthalate, ethyl n-butyl 3-tert-butylphthalate, ethyl n-butyl4-tert-butylphthalate, ethyl n-butyl 4,5-dimethylphthalate, ethyln-butyl 4,5-diethylphthalate, ethyl n-butyl 4-methyl-5-ethylphthalate,ethyl n-butyl 4-ethyl-5-methylphthalate, ethyl isobutyl3-methylphthalate, ethyl isobutyl 4-methylphthalate, ethyl isobutyl3-ethylphthalate, ethyl isobutyl 4-ethylphthalate, ethyl isobutyl3-tert-butylphthalate, ethyl isobutyl 4-tert-butylphthalate, ethylisobutyl 4,5-dimethylphthalate, ethyl isobutyl 4,5-diethyl-phthalate,ethyl isobutyl 4-methyl-5-ethylphthalate, ethyl isobutyl4-ethyl-5-methylphthalate, ethyl isohexyl 3-methylphthalate, ethylisohexyl 4-methylphthalate, ethyl isohexyl 3-ethylphthalate, ethylisohexyl 4-ethylphthalate, ethyl isohexyl 3-tert-butylphthalate, ethylisohexyl 4-tert-butylphthalate, ethyl isohexyl 4,5-dimethylphthalate,ethyl isohexyl 4, 5-diethylphthalate, ethyl isohexyl4-methyl-5-ethylphthalate, ethyl isohexyl 4-ethyl-5-methyl-phthalate,n-butyl isobutyl 3-methylphthalate, n-butyl isobutyl 4-methylphthalate,n-butyl isobutyl 3-ethylphthalate, n-butyl isobutyl 4-ethylphthalate,n-butyl isobutyl 3-tert-butylphthalate, n-butyl isobutyl4-tert-butylphthalate, n-butyl isobutyl 4,5-dimethylphthalate, n-butylisobutyl 4,5-diethylphthalate, n-butyl isobutyl4-methyl-5-ethylphthalate, n-butyl isobutyl 4-ethyl-5-methylphthalate,n-butyl isohexyl 3-methylphthalate, n-butyl isohexyl 4-methylphthalate,n-butyl isohexyl 3-ethylphthalate, n-butyl isohexyl 4-ethyl-phthalate,n-butyl isohexyl 3-tert-butylphthalate, n-butyl isohexyl4-tert-butylphthalate, n-butyl isohexyl 4,5-dimethylphthalate, n-butylisohexyl 4,5-diethylphthalate, n-butyl isohexyl4-methyl-5-ethylphthalate, and n-butyl isohexyl4-ethyl-5-methylphthalate. In the above general formula (1), where n is1 and R¹ is an alkyl of 1 to 5 carbon atoms or n is 2 and R¹ is an alkylgroup of 1 to 5 carbon atoms or halogen atom, and where only one of R²and R³ is an alkyl group of 4 to 8 carbon atoms having a tertiary carbonatom, the following compounds are specifically included: ethyltert-butyl 3-methylphthalate, ethyl tert-butyl 4-methylphthalate, ethyltert-butyl 3-ethylphthalate, ethyl tert-butyl 4-ethylphthalate, ethyltert-butyl 4,5-dimethylphthalate, ethyl tert-butyl 4,5-diethylphthalate,ethyl tert-butyl 4-methyl-5-ethylphthalate, ethyl tert-butyl4-ethyl-5-methylphthalate, ethyl tert-butyl 4-methyl-5-chlorophthalate,ethyl tert-butyl 4-chloro-5-methylphthalate, ethyl tert-butyl4-methyl-5-bromophthalate, ethyl tert-butyl 4-bromo-5-methylphthalate,ethyl tert-butyl 4-ethyl-5-chlorophthalate, ethyl tert-butyl4-chloro-5-ethylphthalate, ethyl tert-butyl 4-ethyl-5-bromophthalate,ethyl tert-butyl 4-bromo-5-ethylphthalate, ethyl neopentyl3-methylphthalate, ethyl neopentyl 4-methylphthalate, ethyl neopentyl3-ethylphthalate, ethyl neopentyl 4-ethylphthalate, ethyl neopentyl4,5-dimethylphthalate, ethyl neopentyl 4,5-diethylphthalate, ethylneopentyl 4-methyl-5-ethylphthalate, ethyl neopentyl4-ethyl-5-methylphthalate, ethyl neopentyl 4-methyl-5-chlorophthalate,ethyl neopentyl 4-chloro-5-methylphthalate, ethyl neopentyl4-methyl-5-bromophthalate, ethyl neopentyl 4-bromo-5-methylphthalate,ethyl neopentyl 4-ethyl-5-chlorophthalate, ethyl neopentyl4-chloro-5-ethylphthalate, ethyl neopentyl 4-ethyl-5-bromophthalate,ethyl neopentyl 4-bromo-5-ethylphthalate, n-butyl neopentyl3-methylphthalate, n-butyl neopentyl 4-methylphthalate, n-butylneopentyl 3-ethylphthalate, n-butyl neopentyl 4-ethylphthalate, n-butylneopentyl 4,5-dimethylphthalate, n-butyl neopentyl 4,5-diethylphthalate,n-butyl neopentyl 4-methyl-5-ethylphthalate, n-butyl neopentyl4-ethyl-5-methylphthalate, n-butyl neopentyl 4-methyl-5-chlorophthalate,n-butyl neopentyl 4-chloro-5-methylphthalate, n-butyl neopentyl4-methyl-5-bromophthalate, n-butyl neopentyl 4-bromo-5-methylphthalate,n-butyl neopentyl 4-ethyl-5-chlorophthalate, n-butyl neopentyl4-chloro-5-ethylphthalate, n-butyl neopentyl 4-ethyl-5-bromophthalate,and n-butyl neopentyl 4-bromo-5-ethylphthalate. In the above generalformula (1), where n is 1 or 2, R¹ is an alkyl group of 6 to 8 carbonatoms, and R² and R³ each is an alkyl group of 4 to 8 carbon atoms bothhaving a tertiary carbon atom, the following compounds are included:di-tert-butyl 4-n-hexylphthalate, di-tert-butyl 4-isohexylphthalate,di-tert-butyl 4-(2,2-dimethylbutyl)-phthalate, di-tert-butyl4-(2,2-dimethylpentyl)phthalate, di-tert-butyl isooctylphthalate,di-tert-butyl 4-n-hexyl-5-chlorophthalate, di-tert-butyl4-n-hexyl-5-bromophthalate, di-tert-butyl 4-isohexyl-5-chlorophthalate,di-tert-butyl 4-isohexyl-5-bromophthalate, di-tert-butyl4-(2,2-dimethyl-butyl)-5-chlorophthalate, di-tert-butyl4-(2,2-dimethyl-butyl)-5-bromophthalate, di-tert-butyl4-(2,2-dimethyl-pentyl)phthalate, di-tert-butyl isooctylphthalate,dineopentyl 4-n-hexylphthalate, dineopentyl 4-isohexyl-phthalate,dineopentyl 4-(2,2-dimethylbutyl)phthalate, dineopentyl4-(2,2-dimethylpentyl)phthalate, dineopentyl isooctylphthalate,dineopentyl 4-n-hexyl-5-chlorophthalate, dineopentyl4-n-hexyl-5-bromophthalate, dineopentyl 4-isohexyl-5-chlorophthalate,dineopentyl 4-isohexyl-5-bromophthalate, dineopentyl4-(2,2-dimethylbutyl)-5-chlorophthalate, dineopentyl4-(2,2-dimethylbutyl)-5-bromophthalate, dineopentyl4-(2,2-dimethylpentyl)phthalate, and dineopentyl isooctylphthalate.

Among these compounds, the followings are preferred: diethyl4-methylphthalate, di-n-butyl 4-methylphthalate, diisobutyl4-methylphthalate, diisohexyl 4-methylphthalate, diisooctyl4-methylphthalate, diethyl 4-ethylphthalate, di-n-butyl4-ethylphthalate, diisobutyl 4-ethylphthalate, diisohexyl4-ethylphthalate, diisooctyl 4-ethylphthalate, diethyl4-tert-butylphthalate, di-n-butyl 4-tert-butyl-phthalate, diisobutyl4-tert-butylphthalate, diisohexyl 4-tert-butylphthalate, diisooctyl4-tert-butylphthalate, diethyl 4,5-dimethylphthalate, di-n-butyl4,5-dimethyl-phthalate, diisohexyl 4,5-dimethylphthalate, diisooctyl4,5-dimethylphthalate, diethyl 4,5-diethylphthalate, di-n-butyl4,5-diethylphthalate, diisohexyl 4,5-diethylphthalate, diisooctyl4,5-diethylphthalate, diethyl 4-methyl-5-chloro-phthalate, diethyl4-methyl-5-bromophthalate, diethyl 4-ethyl-5-chlorophthalate, diethyl4-ethyl-5-bromophthalate, di-n-butyl 4-methyl-5-chlorophthalate,di-n-butyl 4-methyl-5-bromophthalate, di-n-butyl4-ethyl-5-chlorophthalate, di-n-butyl 4-ethyl-5-bromophthalate,diisobutyl 4-methyl-5-chlorophthalate, diisobutyl4-methyl-5-bromophthalate, diisobutyl 4-ethyl-5-chlorophthalate,diisobutyl 4-ethyl-5-bromophthalate, diisohexyl4-methyl-5-chlorophthalate, diisohexyl 4-methyl-5-bromophthalate,diisohexyl 4-ethyl-5-chlorophthalate, diisohexyl4-ethyl-5-bromophthalate, diisooctyl 4-methyl-5-chlorophthalate,diisooctyl 4-methyl-5-bromophthalate, diisooctyl4-ethyl-5-chlorophthalate, and diisooctyl 4-ethyl-5-bromophthalate.

When n is 1 or 2, R¹ is a halogen atom, and at least one of R² and R³ isnot alkyl group of 4 to 8 carbon atoms having a tertiary carbon atom,the following compounds are included: diethyl 3-fluorophthalate, diethyl4-fluorophthalate, diethyl 3-chlorophthalate, diethyl 4-chlorophthalate,diethyl 3-bromophthalate, diethyl 4-bromophthalate, diethyl3-iodo-phthalate, diethyl 4-iodophthalate, diethyl4,5-dichloro-phthalate, diethyl 4,5-dibromophthalate, diethyl4-chloro-5-bromophthalate, di-n-butyl 3-fluorophthalate, di-n-butyl4-fluorophthalate, di-n-butyl 3-chlorophthalate, di-n-butyl4-chlorophthalate, di-n-butyl 3-bromophthalate, di-n-butyl4-bromophthalate, di-n-butyl 3-iodophthalate, di-n-butyl4-iodophthalate, di-n-butyl 4,5-dichlorophthalate, di-n-butyl4,5-dibromophthalate, di-n-butyl 4-chloro-5-bromophthalate, diisobutyl3-fluorophthalate, diisobutyl 4-fluorophthalate, diisobutyl3-chlorophthalate, diisobutyl 4-chlorophthalate, diisobutyl3-bromophthalate, diisobutyl 4-bromophthalate, diisobutyl3-iodophthalate, diisobutyl 4-iodophthalate, diisobutyl4,5-dichlorophthalate, diisobutyl 4,5-dibromophthalate, diisobutyl4-chloro-5-bromophthalate, diisohexyl 3-fluorophthalate, diisohexyl4-fluorophthalate, diisohexyl 3-chlorophthalate, diisohexyl4-chlorophthalate, diisohexyl 3-bromophthalate, diisohexyl4-bromophthalate, diisohexyl 3-iodophthalate, diisohexyl4-iodophthalate, isohexyl 4,5-dichlorophthalate, diisohexyl4,5-dibromophthalate, diisohexyl 4-chloro-5-bromophthalate, diisooctyl3-fluorophthalate, diisooctyl 4-fluorophthalate, diisooctyl3-chlorophthalate, diisooctyl 4-chlorophthalate, diisooctyl3-bromophthalate, diisooctyl 4-bromophthalate, diisooctyl3-iodophthalate, diisooctyl 4-iodophthalate, diisooctyl4,5-dichlorophthalate, diisooctyl 4,5-dibromophthalate, diisooctyl4-chloro-5-bromophthalate, di-n-decyl 4-chlorophthalate, isodecyl4-chlorophthalate, di-n-decyl 4-bromophthalate, isodecyl4-bromophthalate, ethyl n-butyl 3-fluorophthalate, ethyl n-butyl4-fluorophthalate, ethyl n-butyl 3-chlorophthalate, ethyl n-butyl4-chlorophthalate, ethyl n-butyl 3-bromophthalate, ethyl n-butyl4-bromophthalate, ethyl n-butyl 3-iodophthalate, ethyl n-butyl4-iodophthalate, ethyl n-butyl 4,5-dichlorophthalate, ethyl n-butyl4,5-dibromophthalate, ethyl n-butyl 4-chloro-5-bromophthalate, ethylisobutyl 3-fluorophthalate, ethyl isobutyl 4-fluorophthalate, ethylisobutyl 3-chlorophthalate, ethyl isobutyl 4-chlorophthalate, ethylisobutyl 3-bromophthalate, ethyl isobutyl 4-bromophthalate, ethylisobutyl 3-iodophthalate, ethyl isobutyl 4-iodophthalate, ethyl isobutyl4,5-dichlorophthalate, ethyl isobutyl 4,5-dibromophthalate, ethylisobutyl 4-chloro-5-bromophthalate, ethyl isohexyl 3-fluorophthalate,ethyl isohexyl 4-fluorophthalate, ethyl isohexyl 3-chlorophthalate,ethyl isohexyl 4-chlorophthalate, ethyl isohexyl 3-bromo-phthalate,ethyl isohexyl 4-bromophthalate, ethyl isohexyl 3-iodophthalate, ethylisohexyl 4-iodophthalate, ethyl isohexyl 4,5-dichlorophthalate, ethylisohexyl 4,5-dibromo-phthalate, ethyl isohexyl4-chloro-5-bromophthalate, ethyl isobutyl 3-fluorophthalate, ethylisobutyl 4-fluorophthalate, ethyl isobutyl 3-chlorophthalate, ethylisobutyl 4-chlorophthalate, ethyl isobutyl 3-bromophthalate, ethylisobutyl 4-bromophthalate, ethyl isobutyl 3-iodophthalate, ethylisobutyl 4-iodophthalate, ethyl isobutyl 4,5-dichlorophthalate, ethylisobutyl 4,5-dibromophthalate, ethyl isobutyl 4-chloro-5-bromophthalate,n-butyl isobutyl 3-fluorophthalate, n-butyl isobutyl 4-fluorophthalate,n-butyl isobutyl 3-chlorophthalate, n-butyl isobutyl 4-chlorophthalate,n-butyl isobutyl 3-bromophthalate, n-butyl isobutyl 4-bromophthalate,n-butyl isobutyl 3-iodophthalate, n-butyl isobutyl 4-iodophthalate,n-butyl isobutyl 4,5-dichlorophthalate, n-butyl isobutyl4,5-dibromophthalate, n-butyl isobutyl 4-chloro-5-bromophthalate,n-butyl isohexyl 3-fluorophthalate, n-butyl isohexyl 4-fluorophthalate,n-butyl isohexyl 3-chlorophthalate, n-butyl isohexyl 4-chlorophthalate,n-butyl isohexyl 3-bromophthalate, n-butyl isohexyl 4-bromophthalate,n-butyl isohexyl 3-iodophthalate, n-butyl isohexyl 4-iodophthalate,n-butyl isohexyl 4,5-dichlorophthalate, n-butyl isohexyl4,5-dibromophthalate, n-butyl isohexyl 4-chloro-5-bromo-phthalate, ethyltert-butyl 3-fluorophthalate, ethyl tert-butyl 4-fluorophthalate, ethyltert-butyl 3-chlorophthalate, ethyl tert-butyl 4-chlorophthalate, ethyltert-butyl 3-bromo-phthalate, ethyl tert-butyl 4-bromophthalate, ethyltert-butyl 3-iodophthalate, ethyl tert-butyl 4-iodophthalate, ethyltert-butyl 4,5-dichlorophthalate, ethyl tert-butyl 4,5-dibromophthalate,ethyl tert-butyl 4-chloro-5-bromophthalate, ethyl neopentyl3-fluorophthalate, ethyl neopentyl 4-fluorophthalate, ethyl neopentyl3-chlorophthalate, ethyl neopentyl 4-chlorophthalate, ethyl neopentyl3-bromophthalate, ethyl neopentyl 4-bromophthalate, ethyl neopentyl3-iodo-phthalate, ethyl neopentyl 4-iodophthalate, ethyl neopentyl4,5-dichlorophthalate, ethyl neopentyl 4,5-dibromophthalate, ethylneopentyl 4-chloro-5-bromophthalate, n-butyl tert-butyl3-fluorophthalate, n-butyl tert-butyl 4-fluorophthalate, n-butyltert-butyl 3-chlorophthalate, n-butyl tert-butyl 4-chlorophthalate,n-butyl tert-butyl 3-bromophthalate, n-butyl tert-butyl4-bromophthalate, n-butyl tert-butyl 3-iodo-phthalate, n-butyltert-butyl 4-iodophthalate, n-butyl tert-butyl 4,5-dichlorophthalate,n-butyl tert-butyl 4,5-dibromophthalate, n-butyl tert-butyl4-chloro-5-bromophthalate, n-butyl neopentyl 3-fluorophthalate, n-butylneopentyl 4-fluorophthalate, n-butyl neopentyl 3-chlorophthalate,n-butyl neopentyl 4-chlorophthalate, n-butyl neopentyl3-bromo-phthalate, n-butyl neopentyl 4-bromophthalate, n-butyl neopentyl3-iodophthalate, n-butyl neopentyl 4-iodophthalate, n-butyl neopentyl4,5-dichlorophthalate, n-butyl neopentyl 4,5-dibromophthalate, andn-butyl neopentyl 4-chloro-5-bromophthalate.

Among these compounds, preferred are diethyl 4-bromophthalate,di-n-butyl 4-bromophthalate, diisobutyl 4-bromophthalate, diethyl4-chlorophthalate, di-n-butyl 4-chlorophthalate, diisobutyl4-chlorophthalate, diisohexyl 4-chlorophthalate, diisooctyl4-chlorophthalate, diisohexyl 4-bromophthalate, diisooctyl4-bromophthalate, diethyl 4,5-dichlorophthalate, di-n-butyl4,5-dichlorophthalate, diiso-hexyl 4,5-dichlorophthalate, and diisooctyl4,5-dichloro-phthalate.

Among the above specifically described phthalic acid diesters andderivatives thereof, the particularly preferred compound as an electrondonor, one component of the catalyst for olefin polymerization, includesdineopentyl 4-methylphthalate, dineopentyl phthalate, dineopentyl3-fluorophthalate, dineopentyl 4,5-dimethylphthalate, dineopentyl4-bromophthalate, tert-butyl neopentyl phthalate, di-n-butyl4-methylphthalate, di-n-butyl 4-tert-butylphthalate, diethyl4-methylphthalate, diethyl 4-tert-butylphthalate, di-n-butyl4-bromophthalate, di-n-butyl 4-chlorophthalate, di-n-butyl4,5-dichlorophthalate, diisohexyl 4-bromophthalate, and dineopentyl4-tert-butylphthalate. These phthalic acid diesters and derivativesthereof may be used alone or in a combination of two or more.

In the present invention, in addition to the phthalic acid diesters orderivatives thereof as the above component (c), another electron donorcompound may be used in preparation of the component (A). Such anelectron donor compound, which is an organic compound having oxygenand/or nitrogen, includes, for examples, alcohols, phenols, ethers,esters, ketones, acid halides, aldehydes, amines, amides, nitriles,isocyanates, organosilicon compounds containing a Si—O—C linkage, andthe like.

Specifically, these compounds include alcohols such as methanol,ethanol, n-propanol, 2-ethylhexanol, etc., phenols such as phenol,cresol, catechol, etc., ethers such as methyl ether, ethyl ether, propylether, butyl ether, amyl ether, diphenyl ether, etc., monocarboxylicacid esters such as methyl formate, ethyl acetate, vinyl acetate, propylacetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethylbutyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butylbenzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, methylp-toluate, ethyl p-toluate, methyl anisate, ethyl anisate, etc.,dicarboxylic acid esters such as diethylmaleate, dibutyl maleate,dioctyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate,dibutyl adipate, diisodecyl adipate, dioctyl adipate, dimethylphthalate, diethyl phthalate, di-n-propyl phthalate, di-n-butylphthalate, di-isobutyl phthalate, di-n-pentyl phthalate, di-n-hexylphthalate, di-n-heptyl phthalate, di-n-octyl phthalate, di-isooctylphthalate, di-n-nonyl phthalate, di-n-decyl phthalate, etc., ketonessuch as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone,benzophenone, etc., acid halides such as phthalic acid dichloride,terephthalic acid dichloride, etc., aldehydes such as acetaldehyde,propionaldehyde, octylaldehyde, benz-aldehyde, etc., amines such asmethylamine, ethylamine, tributylamine, piperidine, aniline, pyridine,etc., amides such as oleic acid amide, stearic acid amide, etc.,nitriles such as acetonitrile, benzonitrile, tolunitrile, etc.,isocyanates such as methyl isocyanate, ethyl isocyanate, etc.

The organosilicon compound containing a Si—O—C linkage includesphenylalkoxysilanes, alkylalkoxysilanes, phenylalkylalkoxysilanes,cycloalkylalkoxysilane, cycloalkylalkyl alkoxysilane, and the like.

Among the above electron donor compounds, the esters, particularlyphthalic acid diesters, maleic acid diesters and phenols other than thecomponent (c), are preferred.

In preparation of the component (A) in the present invention, inaddition to the above-mentioned essential component, an aluminumcompound such as aluminum trichloride, diethoxy-aluminum chloride,diisopropoxyaluminum chloride, ethoxy-aluminum dichloride,isopropoxyaluminum dichloride, butoxy-aluminum dichloride and (or)triethoxyaluminum, or an organic acid metal salt such as sodiumstearate, magnesium stearate, aluminum stearate, or a polysiloxane suchas chain or partially hydrogenated or cyclic or denatured polysiloxanewhich is liquid or viscous at ordinary temperature, may be used.

The above-mentioned component (A) may be prepared, as mentioned above,by making the component (a), component (b) and component (c) contactwith each other. The contact is preferably carried out in the presenceof an inert organic solvent in view of easiness of operation, though itmay be processed in the absence of the solvent. The inert organicsolvent used includes saturated hydrocarbon compounds such as hexane,heptane and (or) cyclohexane, aromatic hydrocarbon compounds such asbenzene, toluene, xylene and (or) ethylbenzene, and halogenatedhydrocarbon compounds such as o-dichloro-benzene, methylene chloride,carbon tetrachloride and (or) dichloroethane. Among these compounds, anaromatic hydrocarbon compound which is in a liquid state at ordinarytemperature and has the boiling point at approximately 90 to 150° C.,may preferably be used, specifically including toluene, xylene,ethylbenzene, etc.

As for methods for preparing the component (A), the followings areexemplified: a method in which a magnesium compound in the abovecomponent (a) is dissolved in an alcohol or titanium compound and madecontact or heated with the component (b) or the components (b) and (c)to yield a solid component as precipitate; and a method in which thecomponent (a) is suspended in the component (b) or an inert hydrocarbonsolvent, which is then made contact with the component (c) or thecomponents (c) and (b) to yield the component (A).

Among these methods, the particle of solid catalyst component obtainedin the former is nearly spherical and its size distribution is sharp. Inthe latter method, where a spherical magnesium compound is used, a solidcatalyst component of which the particle is spherical and has sharp sizedistribution can be obtained. Moreover, even when no spherical magnesiumcompound is used, similarly, a solid catalyst component of which theparticle is spherical and has sharp size distribution can be obtained byforming the particles by a spray-drying process, for example, spraydrying of a solution or suspension using a sprayer.

The contact of each component may be carried out in a moisture-freecondition under an inert gas atmosphere with stirring in a vesselequipped with a stirrer. The contact temperature, when it is carried outwith simple stirring or under dispersing or suspending for denaturationprocessing, may be in a range of relatively low temperature around roomtemperature. When the product is obtained by reaction after contact,however, the temperature is preferably kept in a range of 40 to 130° C.At a temperature lower than 40° C., the reaction does not proceed well,and consequently produces a solid catalyst component insufficient inperformance. At a temperature over 130° C., it becomes difficult tocontrol the reaction because of markedly increased vaporization of thesolvent used. The reaction is conducted for a period of 1 minute orlonger, preferably 10 minutes or longer, more preferably 30 minutes orlonger.

The method for preparing the component (A) is illustrated as follows.

(1) A method comprises: a solution of magnesium chloride dissolved in atetra-alkoxytitanium is brought into contact with polysiloxane to yielda solid product, which is then allowed to catalitycally react withtitanium tetrachloride and then with the component (c) to yield thecomponent (A). In this reaction, the component (A) may preliminarily betreated with an organoaluminum compound, an organosilicon compound andan olefin for polymerization.

(2) A method in which anhydrous magnesium chloride is allowed to reactwith 2-ethylhexyl alcohol to give a, homogeneous solution, which isbrought into contact with phthalic anhydride. The resulting solution isthen allowed to catalytically react with titanium tetrachloride and thecomponent (c) to yield a solid product, which is further brought intocontact with titanium tetrachloride to yield the component (A).

(3) A method in which metal magnesium, butyl chloride and dibutyl etheris allowed to react to yield an organomagnesium compound, which isallowed to catalytically react with tetrabutoxytitanium andtetraethoxytitanium to give a solid product. The latter is allowed tocatalytically react with the component (c), dibutyl ether and titaniumtetrachloride to yield the component (A). In this reaction, thecomponent (A) may also be prepared by preliminarily treating the solidcomponent with an organoaluminum compound, an organosilicon compound andan olefin for polymerization.

(4) A method in which an organomagnesium compound such asdibutylmagnesium and an organoaluminum compound are allowed tocatalytically react with an alcohol such as butanol and (or)2-ethylhexyl alcohol, in the presence of a hydrocarbon solvent to give ahomogeneous solution. The latter is brought into contact with a siliconcompound such as SiCl₄, HSiCl₃ and/or polysiloxane, to yield a solidproduct. This is then allowed to catalytically react with titaniumtetrachloride and the component (c) in the presence of an aromatichydrocarbon solvent and then brought into contact with titaniumtetrachloride to yield the component (A).

(5) A method in which magnesium chloride, a tetra-alkoxytitanium and analiphatic alcohol are allowed to catalytically react in the presence ofan aliphatic hydrocarbon compound to give a homogeneous solution, towhich is then added titanium tetrachloride. The mixture is then heatedto yield a solid product, which is then allowed to contact with thecomponent (c) and then with titanium tetrachloride to yield thecomponent (A).

(6) A method in which metal magnesium powder, an alkyl monohalidecompound and iodine are subjected to catalytic reaction. The reactionmixture is then allowed to catalytically react with atetraalkoxytitanium, an acid halide and an aliphatic alcohol in thepresence of an aliphatic hydrocarbon to give a homogeneous solution, towhich is then added titanium tetrachloride. The mixture is then heatedto yield a solid product, which is then allowed to contact with thecomponent (c) and then with titanium tetrachloride to yield thecomponent (A).

(7) A method in which diethoxymagnesium is suspended in an alkylbenzeneor halogenated hydrocarbon solvent, then brought into contact withtitanium tetrachloride, and then with the component (c) under heating toyield a solid product. This is washed with an alkylbenzene and thenagain brought into contact with titanium tetrachloride in the presenceof an alkylbenzene to yield the component (A). In this reaction, thecomponent (A) may be prepared by thermal treatment of the solid productin the presence or absence of a hydrocarbon solvent.

(8) A method in which diethoxymagnesium is suspended in an alkylbenzeneand then allowed to catalytically react with titanium tetrachloride andthe component (c) to yield a solid product. This is washed with analkylbenzene and then again brought into contact with titaniumtetrachloride in the presence of an alkylbenzene to yield the component(A). In this reaction, the component (A) may be prepared by contact ofthe solid component with titanium tetrachloride 2 times or more.

(9) A method in which diethoxy magnesium, calcium chloride and a siliconcompound of the formula Si(OR¹⁵)₄ (wherein R¹⁵ is an alkyl group or arylgroup) are pulverized together, and the resulting powder is suspended inan aromatic hydrocarbon. The mixture is allowed to catatlytically reactwith titanium tetrachloride and the component (c) and then furtherbrought into contact with titanium tetrachloride to yield the component(A).

(10) A method in which diethoxy magnesium and the component (c) aresuspended in an alkylbenzene, which is then added to titaniumtetachloride to react to yield a solid product. This is washed with analkylbenzene and then again brought into contact with titaniumtetrachloride in the presence of an alkylbenzene to yield the component(A).

(11) A method in which a calcium halide and a fatty acid magnesium suchas magnesium stearate are allowed to catalytically react with titaniumtetrachloride and the component (c), and then brought into contact withtitanium tetrachloride to yield the component (A).

(12) A method in which diethoxymagnesium is suspended in an alkylbenzeneor halogenated hydrocarbon solvent, then brought into contact withtitanium tetrachloride, and then with the component (c) under heating toyield a solid product. This is washed with an alkylbenzene and thenagain brought into contact with titanium tetrachloride in the presenceof an alkylbenzene to yield the component (A), wherein the reactionmixture is brought into contact with aluminum chloride in any step ofthe above suspending or contact or catalytic reaction.

(13) A method in which diethoxymagnesium, 2-ethylhexyl alcohol andcarbon dioxide are subjected to catalytic reaction to give a homogeneoussolution in the presence of toluene, with which titanium tetra-chlorideand the component (c) are allowed to catalytically react to yield asolid product. This is dissolved in tetrahydrofuran to yield a solidproduct as precipitate, which is allowed to catalytically react withtitanium tetrachloride, if required repeatedly, to yield the component(A). In this reaction, a silicon compound such as tetrabutoxysilane, maybe used in any step of the above-mentioned contact, catalytic reactionand dissolution.

(14) A method in which magnesium chloride, an organic epoxy compound anda phosphoric acid compound are suspended into a hydrocarbon solvent suchas toluene and heated to give a homogeneous solution, which is allowedto catalytically react with phthalic anhydride and titaniumtetrachloride to yield a solid product. This is allowed to catalyticallyreact with the component (c), and the resulting product is washed withanalkylbenzene and then again brought into contact with titaniumtetrachloride in the presence of an alkylbenzene to yield the component(A).

(15) In this method, a dialkoxymagnesium, a titanium compound and thecomponent (c) are subjected to catalytic reaction in the presence oftoluene. The resulting reaction product is allowed to catalyticallyreact with a silicon compound such as polysiloxane, then with titaniumtetrachloride, then with a metal salt of organic acid, and then againwith titanium tetrachloride to yield the component (A).

In a preferred method for preparing the component (A) used in thepresent invention, a dialkoxymagnesium is suspended in an aromatichydrocarbon solvent which is liquid at ordinary temperature, and thenbrought into contact with the component (c) and then with titaniumtetrachloride to yield the component (A). Alternatively, adialkoxymagnesium is suspended in an aromatic hydrocarbon solvent whichis liquid at ordinary temperature, and then brought into contact withtitanium tetrachloride and then with the component (c) to yield thecomponent (A).

The particularly preferred method for preparing the component (A) usedin the present invention is as follows. For example, a dialkoxymagnesiumis suspended in an aromatic hydrocarbon solvent, which is liquid atordinary temperature, to give a suspension, which is brought intocontact with titanium tetrachloride at −20 to 100° C., preferably −10 to70° C., more preferably 0 to 30° C., and then allowed to react at 40 to130° C., more preferably 70 to 120° C. During this operation, before orafter contact with a titanium halide, the above suspension is broughtinto contact with the component (c) at −20 to 130° C. to yield a solidreaction product. This is washed with an aromatic hydrocarbon compound,which is liquid at ordinary temperature, and then again allowed tocatalytically react with titanium tetrachloride in the presence of anaromatic hydrocarbon compound at 40 to 130° C., more preferably at 70 to120° C. The product is further washed with a hydrocarbon compound whichis liquid at ordinary temperature to yield the component (A).

The amount of each compound to be used, though it could not be definedbecause it depends on the preparation method employed, for example, thatof the component (b) is 0.5 to 100 mole, preferably 0.5 to 50 mole, morepreferably 1 to 10 mole, for 1 mole of the component (a). The amount ofthe component (c) is 0.01 to 10 mole, preferably 0.01 to 1 mole, morepreferably 0.02 to 0.6 mole.

The component (A) prepared as mentioned above contains magnesium,titanium, the component (c) and a halogen atom. The content of eachcomponent is but not limited to 10 to 30% by weight of magnesium, 1 to5% by weight of titanium, 1 to 20% by weight of the component (c), and40 to 70% by weight of halogen atom.

The organoaluminum compound (B)(hereinafter sometimes referred to as“component (B)”) used in formation of the catalyst for propylenepolymerization in the present invention includes those represented bythe general formula R⁴ _(p)AlQ_(3−p) (wherein R⁴ is an alkyl group of 1to 4 carbon atoms; Q is hydrogen atom or halogen atom; and p is aninteger of 0<p≦3). Specific example of such an organoaluminum compound(B) includes triethyl aluminum, diethylaluminum chloride,tri-isobutylaluminum, diethyl-aluminum bromide, and diethylaluminumhydride, and these may be used alone or in a combination of two or more.Preferred is triethylaluminum and tri-isobutylaluminum.

The organosilicon compound (C)(hereinafter sometimes referred to as“component (C)”) used in formation of the catalyst for propylenepolymerization in the invention includes those represented by thegeneral formula R⁵ _(q)Si(OR⁶)_(4−q) (wherein R⁵ is the same ordifferent, representing an alkyl group of 1 to 12 carbon atoms,cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or anaralkyl group; R⁶ is the same or different, representing an alkyl groupof 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinylgroup, an allyl group, or an aralkyl group; q is an integer of 0≦q≦3).Such organosilicon compounds include phenyl-alkoxysilanes,alkylalkoxysilanes, phenylalkylalkoxysilanes, cycloalkylalkoxysilanes,cycloalkylalkylalkoxysilanes, and the like.

Specific examples of the above-mentioned organosilicon compoundsinclude: trimethylmethoxysilane, trimethylethoxysilane,tri-n-propylmethoxysilane, tri-n-propylethoxysilane,tri-n-butylmethoxysilane, tri-isobutylmethoxysilane,tri-tert-butylmethoxysilane, tri-n-butylethoxysilane,tricyclohexylmethoxysilane, tricyclohexylethoxysilane,cyclohexyldimethylmethoxysilane, cyclohexyl-diethyl methoxysilane,cyclohexyldiethylethoxysilane, di-methyldimehoxysilane,dimethyldiethoxysilane, di-n-propyl-dimethoxysilane,di-isopropyldimethoxysilane, di-n-propyl-diethoxysilane,di-isopropyldiethoxysilane, di-n-butyl-dimethoxysilane,di-isobutyldimethoxysilane, di-tert-butyl-dimethoxysilane,di-n-butyldiethoxysilane, n-butylmethyl-dimethoxysilane,bis(2-ethylhexyl)dimethoxysilane, bis(2-ethylhexyl)diethoxysilane,dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane,dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane,bis(3-methylcyclohexyl)di-methoxysilane,bis(4-methylcyclohexyl)dimethoxysilane,bis-(3,5-dimethylcyclohexyl)dimethoxysilane,cyclohexylcyclopentyl-dimethoxysilane,cyclohexylcyclopentyldiethoxysilane,cyclohexylcyclopentyldipropoxysilane,3-methylcyclohexyl-cyclopentyldimethoxysilane,4-methylcyclohexylcyclopentyl-dimethoxysilane,3,5-dimethylcyclohexylcyclopentyldimethoxy-silane,3-methylcyclohexylcyclohexyldimethoxysilane,4-methylcyclohexylcyclohexyldimethoxysilane,3,5-dimethyl-cyclohexylcyclohexyldimethoxysilane,cyclopentylmethyl-dimethoxysilane, cyclopentylmethyldiethoxysilane,cyclo-pentylethyldiethoxy silane,cyclopentyl(iso-propyl)dimethoxy-silane,cyclopentyl(iso-butyl)dimethoxysilane, cyclohexyl-methyldimethoxysilane,cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane,cyclohexylethyldiethoxy-silane, cyclohexyl(n-propyl)dimethoxysilane,cyclohexyl-(iso-propyl)dimethoxysilane,cyclohexyl(n-propyl)diethoxy-silane,cyclohexyl(iso-butyl)dimethoxysilane, cyclohexyl(n-butyl)diethoxysilane,cyclohexyl(n-pentyl)dimethoxysilane, cyclohexyl(n-pentyl)diethoxysilane,diphenyldimethoxysilane, diphenyldiethoxysilane,phenylmethyldimethoxysilane, phenylmethyldiethoxysilane,phenylethyldimethoxysilane, phenylethyldiethoxysilane,methyltrimethoxysilane, methyl-triethoxysilane, ethyltrimethoxysilane,ethyltriethoxysilane, n-propyltrimethoxysilane,iso-propyltrimethoxysilane, n-propyltriethoxysilane,iso-propyltriethoxysilane, n-butyl-trimethoxysilane,iso-butyltrimethoxysilane, tert-butyltri-methoxysilane,n-butyltriethoxysilane, 2-ethylhexyltri-methoxysilane,2-ethylhexyltriethoxysilane, cyclopentyl-trimethoxysilane,cyclopentyltriethoxysilane, cyclohexyl-trimethoxysilane,cyclohexyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane,phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane,tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like.Among the above compounds, preferably used aredi-n-propyldimethoxy-silane, di-iso-propyldimethoxysilane,di-n-butyldimethoxy-silane, di-iso-butyldimethoxysilane,di-tert-butyldimethoxy-silane, di-n-butyldiethoxysilane,tert-butyltrimethoxysilane, dicyclohexyldimethoxysilane,dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane,cyclohexylmethyldiethoxy-silane, cyclohexylethyldimethoxysilane,cyclohexylethyldi-ethoxysilane, dicyclopentyl dimethoxysilane,dicyclopentyl-diethoxysilane, cyclopentylmethyldimethoxysilane,cyclo-pentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane,cyclohexylcyclopentyldimethoxysilane,cyclohexylcyclo-pentyldiethoxysilane,3-methylcyclohexylcyclopentyldi-methoxysilane,4-methylcyclohexylcyclopentyldimethoxysilane, and3,5-dimethylcyclohexylcyclopentyldimethoxysilane. The organosiliconcompound (C) may be used alone or in a combination of two or more.

Next, the catalyst for polymerization of olefins of the presentinvention, which are composed of the above-mentioned component (A),component (B) and component (C), are applied to polymerization orco-polymerization of olefins. The olefins include ethylene, propylene,1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like,which may be used alone or in combination of two or more. Particularly,ethylene, propylene and 1-butene are preferably used. Particularlypreferred is propylene. In polymerization of propylene,co-polymerization with another olefin may be achieved. The olefins usedin co-polymerization include ethylene, 1-butene, 1-pentene,4-methyl-1-pentene, vinylcyclohexane, etc., and these olefins may beused alone or in combination of two or more. Particularly ethylene and1-butene are preferably used.

The ratio of the amount of each component to be used may optionally bedetermined as far as it does not effect on the result of the presentinvention. Though there is no particular limitation, the component (B)may be used in a range of 1 to 2000 mole, preferably 50 to 1000 mole,for 1 mole of the component (A). The component (C) may be used in arange of 0.002 to 10 mole, preferably 0.01 to 2 mole, particularly 0.01to 0.5 mole, for 1 mole of the component (B).

Though each component may be brought into contact in optional order, itis desirous that first the organoaluminum compound (B) is placed in apolymerization medium, which is then brought into contact with theorganosilicon compound (C) and then with the solid catalyst component(A).

The polymerization reaction of the present invention may be carried outin the presence or absence of an organic solvent. The olefin monomersuch as propylene, may be used in a state of either gas or liquid. Thepolymerization is made at a temperature of 200° C. or lower, preferably100° C. or lower at a pressure of 10 MPa or lower, preferably 5 MPa orlower. Any method of polymerization such as continuous polymerizationand batch type polymerization may be employed. The polymerizationreaction may be conducted in one-step or two or more steps.

Moreover, in polymerizing an olefin using a catalyst comprising thecomponent (A), component (B) and component (C) (also referred to as mainpolymerization), it is desirous to make preliminary polymerization priorto main polymerization in order to improve much more catalyst activity,stereoregularity and granular properties of the polymer generated. Inthe preliminary polymerization, a monomer such as olefins or styrene maybe used in the same manner as in the main polymerization.

In carrying out the preliminary polymerization, though each componentand monomer may be brought into contact in optional order, it ispreferable that first the component (B) is placed in a reaction mediumfor preliminary polymerization under inert gas atmosphere or such a gasas propylene used in polymerization, and brought into contact with thecomponent (A), and then with an olefin such as propylene and/or one ortwo or more of other olefins. When the preliminary polymerization iscarried out in combination with the component (C), it is desirous thatfirst the component (B) is placed in a reaction medium for preliminarypolymerization under inert gas atmosphere or such a gas as propyleneused in polymerization, and brought into contact with the component (C),and then with the solid catalyst component (A), followed by contact withan olefin such as propylene and/or one or two or more of other olefins.

When an olefin is polymerized in the presence of a catalyst forpolymerization of olefins formed in the present invention, it ispossible to produce an olefin polymer in a much higher yield, while highstereoregularity being retained, than with the catalyst used in theprior art. High responsiveness to hydrogen can also be realized.

WORKING EXAMPLES

The present invention will be illustrated specifically by the followingExamples, compared with Comparative Examples.

Preparation 1

In a 2.0 liter three-necked flask equipped with a refluxing condenserwas introduced 25.0 g of 4-methylphthalic acid and 100.0 g of neopentylalcohol, to which was slowly added 18 ml of sulfuric acid at 66° C., andthe mixture was refluxed at a temperature of 115 to 125° C. for 2 hours.After cooling, the reaction mixture was moved into a separating funnelcontaining 150 ml of distilled water. The flask was washed with 200 mlof diethyl ether, and the ether was poured into the separating funnel.After flashing operation, removal of the aqueous layer (lower layer) wasrepeated 3 times. Then, 150 ml of 5% sodium hydrogen carbonate aqueoussolution was added, and after flashing operation made, the aqueous layershowed pH 7 to 8. After removal of the aqueous layer, the organic layerwas washed with 300 ml of saturated brine and then with 150 ml ofdistilled water. After removal of the aqueous layer, the ether layer(upper layer) was placed in an Erlenmeyer flask and dried on anhydroussodium sulfate. Ether was distilled off under reduced pressure, and theresidue was further distilled under reduced pressure. When temperatureat the column top reached approximately 190° C., 13.0 g of yellowviscous liquid was obtained. This was cooled to about −10° C. to givewhite crystals, which were recrystallized from ethanol to give 11.8 g(26.5% yield) of white crystals in good purity. This white crystallinematerial was analyzed by means of MS, ¹H-NMR and Raman spectra inrespective analyzers as described below and identified to be dineopentyl4-methyl-phthalate. The analytical values are shown in Tables 1 to 3.

Analyzers

MS was measured in an apparatus Finigan Mat (GC-MS), and ¹H-NMR wasmeasured in an apparatus JEOL GSX270, where CDCl₃ was used as solvent.Raman spectra were measured in an apparatus JEOL RFT800.

Preparation 2

In a 2.0 liter three-necked flask equipped with a refluxing condenserwas introduced 50.0 g of 4-bromophthalic acid and 100.1 g of neopentylalcohol, to which was slowly added 36 ml of sulfuric acid at 69° C. Themixture was refluxed at a temperature of 115 to 125° C. for 3.5 hours.After cooling, the reaction mixture was moved into a separating funnelcontaining 600 ml of distilled water. The flask was washed with 500 mlof diethyl ether, and the ether was poured into the separating funnel.After flashing operation, removal of the aqueous layer (lower layer) wasrepeated 3 times. Then, 250 ml of 5% sodium hydrogen carbonate aqueoussolution was added, and after flashing operation made, the aqueous layershowed pH 7 to 8. After removal of the aqueous layer, the organic layerwas washed with 300 ml of saturated brine and then with 150 ml ofdistilled water. After removal of the aqueous layer, the ether layer(upper layer) was placed in an Erlenmeyer flask and dried on anhydroussodium sulfate. Ether was distilled off under reduced pressure, and theresidue was further distilled under reduced pressure. When temperatureat the column top reached approximately 170° C., 61.9 g of light yellowviscous liquid was obtained. This was cooled to about −10° C. to givewhite crystals, which were recrystallized from ethanol to give 33.2 g(39.2% yield) of white crystals in good purity. This white crystallinematerial was identified in respective analyzers in the same manner asdescribed above. As results, this was confirmed to be dineopentyl4-bromophthalate. The analytical values are shown in Tables 1 to 3.

Preparation 3

In a 2.0 liter three-necked flask equipped with a refluxing condenserwas introduced 24.0 g of 3-fluorophthalic acid and 99.6 g of neopentylalcohol, to which was slowly added 18 ml of sulfuric acid at 62° C. Themixture was refluxed at a temperature of 115 to 125° C. for 2 hours.After cooling, the reaction mixture was moved into a separating funnelcontaining 300 ml of distilled water. The flask was washed with 210 mlof diethyl ether, and the ether was poured into the separating funnel.After flashing operation, removal of the aqueous layer (lower layer) wasrepeated 3 times. Then, 150 ml of 5% sodium hydrogen carbonate aqueoussolution was added, and after flashing operation made, the aqueous layershowed pH 7 to 8. After removal of the aqueous layer, the organic layerwas washed with 150 ml of saturated brine and then with 150 ml ofdistilled water. After removal of the aqueous layer, the ether layer(upper layer) was placed in an Erlenmeyer flask and dried on anhydroussodium sulfate. Ether was distilled off under reduced pressure, and theresidue was further distilled under reduced pressure. When temperatureat the column top reached approximately 150° C., 15.3 g of yellowviscous liquid was obtained. This was crystallized from ethanol to give12.0 g (28.4% yield) of white crystals in good purity. This whitecrystalline material was identified in respective analyzers in the samemanner as described above. As results, this was confirmed to bedineopentyl 3-fluorophthalate. The analytical values are shown in Tables1 to 3.

Preparation 4

In a 2.0 liter three-necked flask equipped with a refluxing condenserwas introduced 21.1 g of 4,5-dimethylphthalic acid and 99.7 g ofneopentyl alcohol, to which was slowly added 18 ml of sulfuric acid at67° C. The mixture was refluxed at a temperature of 115 to 125° C. for 2hours. After cooling, the reaction mixture was moved into a separatingfunnel containing 300 ml of distilled water. The flask was washed with210 ml of ethyl ether, and the ether was poured into the separatingfunnel. After flashing operation, removal of the aqueous layer (lowerlayer) was repeated 3 times. Then, 150 ml of 5% sodium hydrogencarbonate aqueous solution was added, and after flashing operation made,the aqueous layer showed pH 7 to 8. After removal of the aqueous layer,the organic layer was washed with 150 ml of saturated brine and thenwith 100 ml of distilled water. After removal of the aqueous layer, theether layer (upper layer) was placed in an Erlenmeyer flask and dried onanhydrous sodium sulfate. Ether was distilled off under reducedpressure, and the residue was further distilled under reduced pressure.When temperature at the column top reached approximately 170° C., 18.9 gof yellow viscous liquid was obtained. This was crystallized fromethanol to give 12.1 g (36.7% yield) of white crystals in good purity.This white crystalline material was identified in respective analyzersin the same manner as described above. As results, this was confirmed tobe dineopentyl 4,5-dimethyl-phthalate. The analytical values are shownin Tables 1 to 3.

Preparation 5

In a 2.0 liter three-necked flask equipped with are fluxing condenserwas introduced 32.6 g of 4-tert-butylphthalic acid and 150.0 g ofneopentyl alcohol, to which was slowly added 36 ml of sulfuric acid at66° C. The mixture was refluxed at a temperature of 115 to 125° C. for 3hours. After cooling, the reaction mixture was moved into a separatingfunnel containing 400 ml of distilled water. The flask was washed with300 ml of diethyl ether, and the ether was poured into the separatingfunnel. After flashing operation, removal of the aqueous layer (lowerlayer) was repeated 3 times. Then, 200 ml of 5% sodium hydrogencarbonate aqueous solution was added, and after flashing operation made,the aqueous layer showed pH 7 to 8. After removal of the aqueous layer,the organic layer was washed with 200 ml of saturated brine and thenwith 150 ml of distilled water. After removal of the aqueous layer, theether layer (upper layer) was placed in an Erlenmeyer flask and dried onanhydrous sodium sulfate. Ether was distilled off under reducedpressure, and the residue was further distilled under reduced pressure.When temperature at the column top reached approximately 170° C., 23.6 g(44.3% yield) of yellow viscous liquid was obtained. This yellow liquidmaterial was identified in respective analyzers in the same manner asdescribed above. As results, this was confirmed to be dineopentyl4-tert-butylphthalate. The analytical values are shown in Tables 1 to 3.

Preparation 6

In a 2.0 liter three-necked flask equipped with a refluxing condenserwas introduced 25.0 g of 4-methylphthalic acid and 100.0 g of n-butylalcohol, to which was slowly added 18 ml of sulfuric acid at 66° C. Themixture was refluxed at a temperature of 115 to 125° C. for 2 hours.After cooling, the reaction mixture was moved into a separating funnelcontaining 150 ml of distilled water. The flask was washed with 200 mlof ethyl ether, and the ether was poured into the separating funnel.After flashing operation, removal of the aqueous layer (lower layer) wasrepeated 3 times. Then, 150 ml of 5% sodium hydrogen carbonate aqueoussolution was added, and after flashing operation made, the aqueous layershowed pH 7 to 8. After removal of the aqueous layer, the organic layerwas washed with 300 ml of saturated brine and then with 150 ml ofdistilled water. After removal of the aqueous layer, the ether layer(upper layer) was placed in an Erlenmeyer flask and dried on anhydroussodium sulfate. Ether was distilled off under reduced pressure, and theresidue was further distilled under reduced pressure. When temperatureat the column top reached approximately 190° C., 13.0 g of yellowviscous liquid was obtained. This was cooled to approximately −10° C. togive white crystals, which were further recrystallized from ethanol togive 11.8 g (26.5% yield) of white crystals in good purity. This whitecrystalline material was analyzed by means of MS, ¹H-NMR and Ramanspectra in respective analyzers as described below. As results, this wasconfirmed to be di-n-butyl 4-methylphthalate. The identification resultsare shown in Tables 1 to 3.

Preparation 7

In a 2.0 liter three-necked flask equipped with a refluxing condenserwas introduced 50.0 g of 4-bromophthalic acid and 100.1 g of n-butylalcohol, to which was slowly added 36 ml of sulfuric acid at 69° C. Themixture was refluxed at a temperature of 115 to 125° C. for 3.5 hours.After cooling, the reaction mixture was moved into a separating funnelcontaining 600 ml of distilled water. The flask was washed with 500 mlof diethyl ether, and the ether was poured into the separating funnel.After flashing operation, removal of the aqueous layer (lower layer) wasrepeated 3 times. Then, 250 ml of 5% sodium hydrogen carbonate aqueoussolution was added, and after flashing operation made, the aqueous layershowed pH 7 to 8. After removal of the aqueous layer, the organic layerwas washed with 300 ml of saturated brine and then with 150 ml ofdistilled water. After removal of the aqueous layer, the ether layer(upper layer) was placed in an Erlenmeyer flask and dried on anhydroussodium sulfate. Ether was distilled off under reduced pressure, and theresidue was further distilled under reduced pressure. When temperatureat the column top reached approximately 170° C., 61.9 g of light yellowviscous liquid was obtained. This was cooled to approximately −10° C. togive white crystals, which were further recrystallized from ethanol togive 33.2 g (39.2% yield) of white crystals in good purity. This whitecrystalline material was identified in respective analyzers in the samemanner as described above. As results, this was confirmed to bedi-n-butyl 4-bromophthalate. The identification results are shown inTables 1 to 3.

Preparation 8

In a 2.0 liter three-necked flask equipped with a refluxing condenserwas introduced 32.6 g of 4-tert-butylphthalic acid and 100.0 g ofn-butyl alcohol, to which was slowly added 36 ml of sulfuric acid at 66°C. The mixture was refluxed at a temperature of 115 to 125° C. for 3hours. After cooling, the reaction mixture was moved into a separatingfunnel containing 400 ml of distilled water. The flask was washed with300 ml of diethyl ether, and the ether was poured into the separatingfunnel. After flashing operation, removal of the aqueous layer (lowerlayer) was repeated 3 times. Then, 200 ml of 5% sodium hydrogencarbonate aqueous solution was added, and after flashing operation made,the aqueous layer showed pH 7 to 8. After removal of the aqueous layer,the organic layer was washed with 200 ml of saturated brine and thenwith 150 ml of distilled water. After removal of the aqueous layer, theether layer (upper layer) was placed in an Erlenmeyer flask and dried onanhydrous sodium sulfate. Ether was distilled off under reducedpressure, and the residue was further distilled under reduced pressure.When temperature at the column top reached approximately 170° C., 20.5 g(43.3% yield) of yellow viscous liquid was obtained. This yellow liquidwas identified in respective analyzers in the same manner as describedabove. As results, this was confirmed to be di-n-butyl4-tert-butylphthalate. The analytical values are shown in Tables 1 to 3.

Preparation 9

In a 2.0 liter three-necked flask equipped with a refluxing condenserwas introduced 25.0 g of 4-methylphthalic acid and 100.0 g of ethylalcohol, to which was slowly added 36 ml of sulfuric acid at 66° C. Themixture was refluxed at a temperature of 115 to 125° C. for 3 hours.After cooling, the reaction mixture was moved into a separating funnelcontaining 400 ml of distilled water. The flask was washed with 300 mlof diethyl ether, and the ether was poured into the separating funnel.After flashing operation, removal of the aqueous layer (lower layer) wasrepeated 3 times. Then, 200 ml of 5% sodium hydrogen carbonate aqueoussolution was added, and after flashing operation made, the aqueous layershowed pH 7 to 8. After removal of the aqueous layer, the organic layerwas washed with 200 ml of saturated brine and then with 150 ml ofdistilled water. After removal of the aqueous layer, the ether layer(upper layer) was placed in an Erlenmeyer flask and dried on anhydroussodium sulfate. Ether was distilled off under reduced pressure, and theresidue was further distilled under reduced pressure. When temperatureat the column top reached approximately 170° C., 12.5 g (37.5% yield) ofyellow viscous liquid was obtained. This yellow liquid was identified inrespective analyzers in the same manner as described above. As results,this was confirmed to be diethyl 4-methylphthalate. The analyticalvalues are shown in Tables 1 to 3.

Preparation 10

In a 2.0 liter three-necked flask equipped with are fluxing condenserwas introduced 32.6 g of 4-tert-butylphthalic acid and 100.0 g of ethylalcohol, to which was slowly added 36 ml of sulfuric acid at 66° C. Themixture was refluxed at a temperature of 115 to 125° C. for 3 hours.After cooling, the reaction mixture was moved into a separating funnelcontaining 400 ml of distilled water. The flask was washed with 300 mlof diethyl ether, and the ether was poured into the separating funnel.After flashing operation, removal of the aqueous layer (lower layer) wasrepeated 3 times. Then, 200 ml of 5% sodium hydrogen carbonate aqueoussolution was added, and after flashing operation made, the aqueous layershowed pH 7 to 8. After removal of the aqueous layer, the organic layerwas washed with 200 ml of saturated brine and then with 150 ml ofdistilled water. After removal of the aqueous layer, the ether layer(upper layer) was placed in an Erlenmeyer flask and dried on anhydroussodium sulfate. Ether was distilled off under reduced pressure, and theresidue was further distilled under reduced pressure. When temperatureat the column top reached approximately 170° C., 18.5 g (45.3% yield) ofyellow viscous liquid was obtained. This yellow liquid was identified inrespective analyzers in the same manner as described above. As results,this was confirmed to be diethyl 4-tert-butylphthalate. The analyticalvalues are shown in Tables 1 to 3.

Preparation 11

In a 2.0 liter three-necked flask equipped with are fluxing condenserwas introduced 30.0 g of 4-chlorophthalic acid and 100.0 g of n-butylalcohol, to which was slowly added 36 ml of sulfuric acid at 66° C. Themixture was refluxed at a temperature of 115 to 125° C. for 3 hours.After cooling, the reaction mixture was moved into a separating funnelcontaining 400 ml of distilled water. The flask was washed with 300 mlof diethyl ether, and the ether was poured into the separating funnel.After flashing operation, removal of the aqueous layer (lower layer) wasrepeated 3 times. Then, 200 ml of 5% sodium hydrogen carbonate aqueoussolution was added, and after flashing operation made, the aqueous layershowed pH 7 to 8. After removal of the aqueous layer, the organic layerwas washed with 200 ml of saturated brine and then with 150 ml ofdistilled water. After removal of the aqueous layer, the ether layer(upper layer) was placed in an Erlenmeyer flask and dried on anhydroussodium sulfate. Ether was distilled off under reduced pressure, and theresidue was further distilled under reduced pressure. When temperatureat the column top reached approximately 170° C., 18.5 g (39.1% yield) ofyellow viscous liquid was obtained. This yellow liquid was identified inrespective analyzers in the same manner as described above. As results,this was confirmed to be di-n-butyl 4-chlorophthalate. The analyticalvalues are shown in Tables 1 to 3.

Preparation 12

In a 2.0 liter three-necked flask equipped with are fluxing condenserwas introduced 33.0 g of 4,5-dichlorophthalic acid and 100.0 g ofn-butyl alcohol, to which was slowly added 36 ml of sulfuric acid at 66°C. The mixture was refluxed at a temperature of 115 to 125° C. for 3hours. After cooling, the reaction mixture was moved into a separatingfunnel containing 400 ml of distilled water. The flask was washed with300 ml of diethyl ether, and the ether was poured into the separatingfunnel. After flashing operation, removal of the aqueous layer (lowerlayer) was repeated 3 times. Then, 200 ml of 5% sodium hydrogencarbonate aqueous solution was added, and after flashing operation made,the aqueous layer showed pH 7 to 8. After removal of the aqueous layer,the organic layer was washed with 200 ml of saturated brine and thenwith 150 ml of distilled water. After removal of the aqueous layer, theether layer (upper layer) was placed in an Erlenmeyer flask and dried onanhydrous sodium sulfate. Ether was distilled off under reducedpressure, and the residue was further distilled under reduced pressure.When temperature at the column top reached approximately 170° C., 16.3 g(33.0% yield) of yellow viscous liquid was obtained. This yellow liquidwas identified in respective analyzers in the same manner as describedabove. As results, this was confirmed to be di-n-butyl4,5-dichlorophthalate. The analytical values are shown in Tables 1 to 3.

Preparation 13

In a 2.0 liter three-necked flask equipped with are fluxing condenserwas introduced 50.0 g of 4-bromophthalic acid and 100.0 g of isohexylalcohol, to which was slowly added 36 ml of sulfuric acid at 66° C. Themixture was refluxed at a temperature of 115 to 125° C. for 3 hours.After cooling, the reaction mixture was moved into a separating funnelcontaining 400 ml of distilled water. The flask was washed with 300 mlof diethyl ether, and the ether was poured into the separating funnel.After flashing operation, removal of the aqueous layer (lower layer) wasrepeated 3 times. Then, 200 ml of 5% sodium hydrogen carbonate aqueoussolution was added, and after flashing operation made, the aqueous layershowed pH 7 to 8. After removal of the aqueous layer, the organic layerwas washed with 200 ml of saturated brine and then with 150 ml ofdistilled water. After removal of the aqueous layer, the ether layer(upper layer) was placed in an Erlenmeyer flask and dried on anhydroussodium sulfate. Ether was distilled off under reduced pressure, and theresidue was further distilled under reduced pressure. When temperatureat the column top reached approximately 170° C., 35.5 g (42.1% yield) ofyellow viscous liquid was obtained. This yellow liquid was identified inrespective analyzers in the same manner as described above. As results,this was confirmed to be diisohexyl 4-bromophthalate. The analyticalvalues are shown in Tables 1 to 3.

TABLE 1 MS (Mw/z) Molecular Distinct Preparation Compound Name peak peak1 Dineopentyl 4-methylphthalate 320 163 2 Dineopentyl 4-bromophthalate384, 386 184, 182 3 Dineopentyl 3-fluorophthalate 324 167 4 Dineopentyl4,5-dimethylphthalate 334 177 5 Dineopentyl 4-tert-butylphthalate 362205 6 Di-n-butyl 4-methylphthalate 292 163 7 Di-n-butyl 4-bromophthalate356, 358 227, 229 8 Di-n-butyl 4-tert-butylphthalate 334 205 9 Diethyl4-methylphthalate 236 163 10 Diethyl 4-tert-butylphthalate 278 205 11Di-n-butyl 4-chlorophthalate 312 183 12 Di-n-butyl 4,5-dichlorophthalate346, 348 217 13 Diisohexyl 4-bromophthalate 412, 414 182, 184

TABLE 2 ¹H-NMR (ppm; Int) Preparation Compound Name CH₃ al CH₃ ar CH₂Aromatic ring 1 Dineopentyl 4-methylphthalate 1.0s: 18.1 2.4s: 3.0 4.0s:4.0 7.3-7.7m: 3.0 2 Dineopentyl 4-bromophthalate 1.0s: 18.0 — 4.0d: 4.07.6-7.8m: 3.0 3 Dineopentyl 3-fluorophthalate 1.0d: 18.0 — 4.0s: 2.07.3-7.8m: 3.0 4.1s: 2.0 4 Dineopentyl 4,5-dimethylphthalate 1.0s: 18.02.4s: 6.0 4.0s: 4.0 7.6s: 2.0 5 Dineopentyl 4-t-butylphthalate 1.0d:18.0 — 4.0d: 4.0 7.3-7.8m: 3.0 1.3s: 9.0 6 Di-n-butyl 4-methylphthalate1.0t: 6.0 2.4s: 3.0 1.4q: 4.1 7.3-7.8m: 3.0 1.7m: 4.0 4.3m: 4.0 7Di-n-butyl 4-bromophthalate 1.0td: 6.1 — 1.4q: 4.1 7.2-7.8m: 2.9 1.7m:4.1 4.3td: 4.0 8 Di-n-butyl 4-t-butylphthalate 1.0t: 6.0 — 1.4m: 4.07.3-7.8m: 3.0 1.3s: 9.0 1.7m: 4.1 4.3t: 4.0 9 Diethyl 4-methylphthalate1.4t: 6.0 2.4s: 3.0 4.4g: 4.0 7.9s: 3.0 10 Diethyl 4-tert-butylphthalate1.3s: 9.0 — 4.4q: 4.0 7.3-7.8m: 3.0 1.4t: 6.0 11 Di-n-butyl4-chlorophthalate 1.0t: 6.0 — 1.4m: 4.0 7.5-7.8m: 3.0 1.7m: 4.0 4.3t:4.0 12 Di-n-butyl 4,5-dichlorophthalate 1.0t: 6.0 — 1.4m: 4.0 7.9s: 2.01.7m: 4.0 4.3t: 4.0 13 Diisohexyl 4-bromophthalate 0.9d: 12.0 —1.0-1.8m: 2.1 7.2-7.8m: 3.0 1.3m: 4.0 1.6m: 3.9 3.6t: 4.0

TABLE 3 Elemental Analysis (%) Raman (cm⁻¹) Found/Calcd. PreparationCompound Name C═O C-Car Cal-H C H O 1 Dineopentyl 4-methylphthalate 17241612 2963 71.1/71.2 8.8/8.8 20.0/20.0 2923 2 Dineopentyl4-bromophthalate 1730 1593 2962 56.1/56.1 6.2/6.5 16.6/16.6 2940 3Dineopentyl 3-fluorophthalate 1728 1610 2960 66.7/66.6 8.1/7.8 20.2/19.72908 4 Dineopentyl 4,5-dimethylphthalate 1720 1613 2965 71.8/71.88.9/9.0 19.2/19.1 2927 5 Dineopentyl 4-t-butylphthalate 1724 1612 296272.8/72.9 9.3/9.5 17.8/17.7 2918 6 Di-n-butyl 4-methylphthalate 17221608 2913 69.8/69.8 8.2/8.2 20.7/21.9 2873 7 Di-n-butyl 4-bromophthalate1724 1589 2976 54.1/53.8 5.9/5.9 15.7/17.9 2937 8 Di-n-butyl4-t-butylphthalate 1726 1606 2960 71.8/71.8 9.0/9.0 18.9/19.1 2908 9Diethyl 4-methylphthalate 1722 1610 2951 66.2/66.1 6.7/6.8 27.1/27.12911 10 Diethyl 4-tert-butylphthalate 1724 1606 2968 68.8/69.0 8.1/8.022.9/23.0 2937 11 Di-n-butyl 4-chlorophthalate 1726 1593 2935 60.9/61.46.7/6.8 19.8/20.5 2907 2910 12 Di-n-butyl 4,5-dichlorophthalate 17301589 2935 55.5/55.3 5.9/5.8 18.2/18.4 2911 2873 13 Diisohexyl4-bromophthalate 1724 1592 2971 57.9/58.1 7.2/7.1 19.1/19.3 2940 2871

EXAMPLE 1

Preparation of the Solid Catalyst Component (A)

In a 500 ml round bottomed flask equipped with a stirrer, andsubstituted enough with nitrogen gas, was placed 10 g ofdiethoxymagnesium and 80 ml of toluene to give a suspension. To thissuspension was added 20 ml of titanium tetrachloride, and the mixturewas heated up to 80° C. At this point, a solution of 3.5 g ofdineopentyl 4-methylphthalate prepared in Preparation 1 in 3.5 ml oftoluene was added, and the mixture was further heated up to 110° C.Then, the mixture was kept at 110° C. with stirring for 1 hour. Afterthe reaction completion, the mixture was washed 3 times with 100 ml oftoluene at 90° C., and an additional 20 ml of titanium tetrachloride and80 ml of toluene were added, heated up to 110° C., and stirred for 1hour. After the reaction completion, the reaction mixture was washed 7times with 100 ml of n-heptane at 40° C. to yield a solid catalystcomponent. After solid-liquid separation from the solid catalystcomponent, the titanium content in the solid portion was determined tobe 2.8% by weight.

Formation of a Polymerization Catalyst and Polymerization

Into a 2.0 liter autoclave equipped with a stirrer and substitutedcompletely with nitrogen gas, was loaded 1.32 mmole of triethylaluminum,0.13 mmole of cyclohexylmethyl-dimethoxysilane and 0.0026 mmole (astitanium atom) of the above solid catalyst component to yield a catalystfor polymerization. Then, 2.0 liter of hydrogen gas and 1.4 liter ofliquid propylene were loaded, then pre-polymerized at 20° C. for 5minutes, and polymerized under heating at 70° C. for 1 hour. Thepolymerization activity of the solid catalyst component was 60,100 g/gcomponent. The melt index (MI) value of the polymer (a) (measuredaccording to ASTM D 1238 and JIS K 7210) was 19 g/10 min. Thepolymerization activity for the solid catalyst component used herein wascalculated from the following equation: polymerization activity=(a)270.9 (g)/0.00451 (g) of the solid catalyst component.

When this polymer was extracted with boiling n-heptane for 6 hours, theamount of the polymer (b) insoluble in n-heptane was 263.0 g, and then-heptane-insoluble portion of the polymer was 97.5% by weight. Thepolymerization activity, heptane-insoluble portion (HI), and melt index(MI) are shown together in Table 4.

EXAMPLE 2

A solution of 3.4 g of dineopentyl phthalate dissolved in 10.2 ml oftoluene was used in place of a solution of 3.5 g of dineopentyl4-methylphthalate dissolved in 3.5 ml of toluene. Otherwise in the samemanner as in Example 1, the solid component was prepared and applied toformation of a polymerization catalyst and polymerization. The resultingsolid catalyst component contains 3.6% by weight of titanium. The resultof polymerization is shown in Table 4.

EXAMPLE 3

A solution of 3.5 g of dineopentyl 3-fluorophthalate prepared inPreparation 3 dissolved in 4.7 ml of toluene was used in place of asolution of 3.5 g of dineopentyl 4-methylphthalate dissolved in 3.5 mlof toluene. Otherwise in the same manner as in Example 1, the solidcomponent was prepared and applied to formation of a polymerizationcatalyst and polymerization. The resulting solid catalyst componentcontains 3.2% by weight of titanium. The result of polymerization isshown in Table 4.

EXAMPLE 4

In place of 3.5 g dineopentyl 4-methylphthalate, 3.6 g of dineopentyl4,5-dimethylphthalate prepared in Preparation 4 was used. Otherwise inthe same manner as in Example 1, the solid component was prepared andapplied to formation of a polymerization catalyst and polymerization.The resulting solid catalyst component contains 3.6% by weight oftitanium. The result of polymerization is shown in Table 4.

EXAMPLE 5

A solution of 4.2 g of dineopentyl 4-bromophthalate prepared inPreparation 2 dissolved in 5.3 ml of toluene was used in place of asolution of 3.5 g of dineopentyl 4-methylphthalate dissolved in 3.5 mlof toluene. Otherwise in the same manner as in Example 1, the solidcomponent was prepared and applied to formation of a polymerizationcatalyst and polymerization. The resulting solid catalyst componentcontains 2.9% by weight of titanium. The result of polymerization isshown in Table 4.

EXAMPLE 6

A solution of 3.2 g of tert-butyl neopentyl phthalate dissolved in 9.6ml of toluene was used in place of a solution of 3.5 g of dineopentyl4-methylphthalate dissolved in 3.5 ml of toluene. Otherwise in the samemanner as in Example 1, the solid component was prepared and applied toformation of a polymerization catalyst and polymerization. The resultingsolid catalyst component contains 3.8% by weight of titanium. The resultof polymerization is shown in Table 4.

COMPARATIVE EXAMPLE 1

In place of 3.5 g of dineopentyl 4-methylphthalate, 3.0 g ofdi-n-butylphthalate was used. Otherwise in the same manner as in Example1, the solid component was prepared and applied to formation of apolymerization catalyst and polymerization. The resulting solid catalystcomponent contains 3.0% by weight of titanium. The result ofpolymerization is shown in Table 4.

COMPARATIVE EXAMPLE 2

In place of 3.5 g of dineopentyl 4-methylphthalate, 3.4 g of di-n-pentylphthalate was used. Otherwise in the same manner as in Example 1, thesolid component was prepared and applied to formation of apolymerization catalyst and polymerization. The resulting solid catalystcomponent contains 2.6% by weight of titanium. The result ofpolymerization is shown in Table 4.

TABLE 4 Polymern. Activity HI MI (g-pp/g-cat.) (% by weight) (g/10 min)Example 1 60,100 97.5 19 Example 2 60,600 98.6 10 Example 3 58,000 96.918 Example 4 60,900 97.3 22 Example 5 60,800 97.1 25 Example 6 71,30097.2 16 Comp. Ex. 1 42,400 98.7 6.6 Comp. Ex. 2 46,400 97.9 10

EXAMPLE 7

Preparation of the Solid Catalyst Component (A)

In a 500 ml round bottomed flask equipped with a stirrer, andsubstituted enough with nitrogen gas, was placed 10 g ofdiethoxymagnesium and 80 ml of toluene to give a suspension. To thissuspension was added 20 ml of titanium tetrachloride, and the mixturewas heated up to 80° C. At this point, 3.2 g of di-n-butyl4-methylphthalate prepared in Preparation 6 was added, and the mixturewas further heated up to 110° C. Then, the mixture was kept at 110° C.with stirring for 1 hour. After the reaction completion, the mixture waswashed 3 times with 100 ml of toluene at 90° C., and an additional 20 mlof titanium tetrachloride and 80 ml of toluene were added, heated up to110° C., and stirred for 1 hour. After the reaction completion, thereaction mixture was washed 7 times with 100 ml of n-heptane at 40° C.to yield a solid catalyst component. After solid-liquid separation fromthe solid catalyst component, the titanium content in the solid portionwas determined to be 3.2% by weight.

Formation of a Polymerization Catalyst and Polymerization

Polymerization was carried out in the same manner as in Example 1. Theresults are shown in Table 5.

EXAMPLE 8

In place of 3.2 g of di-n-butyl 4-methylphthalate, 3.7 g of di-n-butyl4-tert-butylphthalate prepared in Preparation 8 was used. Otherwise inthe same manner as in Example 7, the solid component was prepared andapplied to formation of a polymerization catalyst and polymerization.The resulting solid catalyst component contains 3.3% by weight oftitanium. The result of polymerization is shown together in Table 5.

EXAMPLE 9

In place of 3.2 g of di-n-butyl 4-methylphthalate, 2.5 g of diethyl4-methylphthalate prepared in Preparation 9 was used. Otherwise in thesame manner as in Example 7, the solid component was prepared andapplied to formation of a polymerization catalyst and polymerization.The resulting solid catalyst component contains 3.1% by weight oftitanium. The result of polymerization is shown together in Table 5.

EXAMPLE 10

In place of 3.2 g of di-n-butyl 4-methylphthalate, 3.0 g of diethyl4-tert-butylphthalate prepared in Preparation 10 was used. Otherwise inthe same manner as in Example 7, the solid component was prepared andapplied to formation of a polymerization catalyst and polymerization.The resulting solid catalyst component contains 3.4% by weight oftitanium. The result of polymerization is shown together in Table 5.

EXAMPLE 11

In the same manner as in Example 7, the solid component was prepared,and 0.13 mmole of dicyclopentyldimethoxysilane (DCPDMS) as anorganosilicon compound was used in place of 0.13 mmole ofcyclohexylmethyldimethoxysilane (CMDMS) in formation of thepolymerization catalyst. Otherwise in the same manner as in Example 1,the polymerization catalyst was formed and applied to polymerization.The result of polymerization is shown together in Table 5.

EXAMPLE 12

In the same manner as in Example 7, the solid component was prepared,and 0.13 mmole of diisopropyldimethoxysilane (DIPDMS) as anorganosilicon compound was used in place of 0.13 mmole ofcyclohexylmethyldimethoxysilane (CMDMS) in formation of thepolymerization catalyst. Otherwise in the same manner as in Example 1,the polymerization catalyst was formed and applied to polymerization.The result of polymerization is shown together in Table 5.

COMPARATIVE EXAMPLE 3

In the same manner as in Comparative Example 1, the solid component wasprepared, and 0.13 mmole of dicyclopentyldi-methoxysilane (DCPDMS) as anorganosilicon compound was used in place of 0.13 mmole ofcyclohexylmethyldimethoxysilane (CMDMS) in formation of thepolymerization catalyst. Otherwise in the same manner as in ComparativeExample 1, the polymerization catalyst was formed and applied topolymerization. The result of polymerization is shown together in Table5.

COMPARATIVE EXAMPLE 4

In the same manner as in Comparative Example 1, the solid component wasprepared, and 0.13 mmole of diisopropyldi-methoxysilane (DIPDMS) as anorganosilicon compound was used in place of 0.13 mmole ofcyclohexylmethyldimethoxysilane (CMDMS) in formation of thepolymerization catalyst. Otherwise in the same manner as in ComparativeExample 1, the polymerization catalyst was formed and applied topolymerization. The result of polymerization is shown together in Table5.

TABLE 5 Polymern. Activity HI MI Organosilicon (g/g-cat) (% by weight)(g/10 min) compound Example 7 50,300 98.6 14 CMDMS Example 8 47,200 98.017 CMDMS Example 9 52,000 98.9 13 CMDMS Example 10 47,900 98.3 13 CMDMSExample 11 57,100 99.1 7.0 DCPDMS Example 12 53,200 98.9 11 DIPDMS Comp.Ex. 3 52,900 99.1 3.6 DCPDMS Comp. Ex. 4 47,500 98.7 6.8 DIPDMS

EXAMPLE 13

Preparation of the Solid Catalyst Component (A)

In a 500 ml round bottomed flask equipped with a stirrer, andsubstituted enough with nitrogen gas, was placed 10 g ofdiethoxymagnesium and 80 ml of toluene to give a suspension. To thissuspension was added 20 ml of titanium tetrachloride, and the mixturewas heated up to 80° C. At this point, 3.9 g of di-n-butyl4-bromophthalate prepared in Preparation 7 was added, and the mixturewas further heated up to 110° C. Then, the mixture was kept at 110° C.with stirring for 1 hour. After the reaction completion, the mixture waswashed 3 times with 100 ml of toluene at 90° C., and an additional 20 mlof titanium tetrachloride and 80 ml of toluene were added, heated up to110° C., and stirred for 1 hour. After the reaction completion, thereaction mixture was washed 7 times with 100 ml of n-heptane at 40° C.to yield a solid catalyst component. After solid-liquid separation fromthe solid catalyst component, the titanium content in the solid portionwas determined to be 2.6% by weight.

Formation of a Polymerization Catalyst and Polymerization

Polymerization was carried out in the same manner as in Example 1. Theresults are shown in Table 6.

EXAMPLE 14

In place of 3.9 g of di-n-butyl 4-bromophthalate, 3.2 g of di-n-butyl4-chlorophthalate prepared in Preparation 11 was used. Otherwise in thesame manner as in Example 13, the solid component was prepared andapplied to formation of a polymerization catalyst and polymerization.The resulting solid catalyst component contains 3.3% by weight oftitanium. The result of polymerization is shown together in Table 6.

EXAMPLE 15

In place of 3.9 g of di-n-butyl 4-bromophthalate, 3.8 g of di-n-butyl4,5-dichlorophthalate prepared in Preparation 12 was used. Otherwise inthe same manner as in Example 13, the solid component was prepared andapplied to formation of a polymerization catalyst and polymerization.The resulting solid catalyst component contains 3.0% by weight oftitanium. The result of polymerization is shown together in Table 6.

EXAMPLE 16

In place of 3.9 g of di-n-butyl 4-bromophthalate, 4.5 g of diisohexyl4-bromophthalate prepared in Preparation 13 was used. Otherwise in thesame manner as in Example 13, the solid component was prepared andapplied to formation of a polymerization catalyst and polymerization.The resulting solid catalyst component contains 2.9% by weight oftitanium. The result of polymerization is shown together in Table 6.

EXAMPLE 17

In the same manner as in Example 13, the solid component was prepared,and 0.13 mmole of dicyclopentyldimethoxysilane (DCPDMS) as anorganosilicon compound was used in place of 0.13 mmole ofcyclohexylmethyldimethoxysilane (CMDMS) in formation of thepolymerization catalyst. Otherwise in the same manner as in Example 1,the polymerization catalyst was formed and applied to polymerization.The result of polymerization is shown together in Table 6.

EXAMPLE 18

In the same manner as in Example 13, the solid component was prepared,and 0.13 mmole of diisopropyldimethoxysilane (DIPDMS) as anorganosilicon compound was used in place of 0.13 mmole ofcyclohexylmethyldimethoxysilane (CMDMS) information of thepolymerization catalyst. Otherwise in the same manner as in Example 1,the polymerization catalyst was formed and applied to polymerization.The result of polymerization is shown together in Table 6.

TABLE 6 Polymern. Activity HI MI Organosilicon (g/g-cat) (% by weight)(g/10 min) compound Example 13 49,800 98.5 13 CMDMS Example 14 47,20098.2 15 CMDMS Example 15 43,900 97.9 21 CMDMS Example 16 49,400 98.0 18CMDMS Example 17 54,400 99.0 7.5 DCPDMS Example 18 53,500 98.8 12 DIPDMS

From the results as shown in Tables 4, 5 and 6, it is found that theolefin polymers can be produced in very high yield by effectingpolymerization of olefins using the solid catalyst component andcatalyst of the present invention. It is also found that theresponsiveness to hydrogen is very high.

Industrial Applicability

The catalysts for olefin polymerization of the present invention canafford polymers of olefins in very high yield while highly retaininghigh stereoregularity. They also have a high responsiveness to hydrogen.Accordingly, they can provide all-purpose polyolefins on a low cost andare expected useful in production of copolymers of olefins having highlyfunctional properties.

What is claimed is:
 1. A solid catalyst component for polymerization ofolefins, which comprises (a) a magnesium compound, (b) titaniumtetrachloride, and (c) a derivative of phthalic acid diester of thefollowing general formula (1):

wherein R¹ is an alkyl group of 1 to 8 carbon atoms or a halogen atom;R² and R³ are the same or different, representing an alkyl group of 1 to12 carbon atoms; the number n of the substituent R¹ is 1 or 2, and whenn is 2, R¹ may be the same or different.
 2. A solid catalyst componentfor polymerization of olefins as claimed in claim 1, wherein saidmagnesium compound is a dialkoxymagnesium.
 3. A solid catalyst componentfor polymerization of olefins as claimed in claim 1, wherein in saidgeneral formula (1), when n is 1, R¹ is a methyl group or a tert-butylgroup, or when n is 2, at least one of R¹ is a methyl group or atert-butyl group.
 4. A solid catalyst component for polymerization ofolefins as claimed in claim 1, wherein in said general formula (1), whenn is 1 or 2, R¹ is a chlorine atom, a bromine atom or a fluorine atom.5. A solid catalyst component for polymerization of olefins as claimedin claim 1, wherein in said general formula (1), when n is 1 or 2, R¹ issubstituted at least for the hydrogen atom at the 4 or 5 position of thebenzene ring.
 6. A solid catalyst component for polymerization ofolefins as claimed in claim 1, wherein in said general formula (1), atleast one of R² and R³ is an alkyl group of 4 to 8 carbon atoms having atertiary carbon atom.
 7. A solid catalyst component for polymerizationof olefins as claimed in claim 1, wherein in said general formula (1),at least one of R² and R³ is a neopentyl group, or at least one of R²and R³ is a tert-butyl group.
 8. A solid catalyst component forpolymerization of olefins as claimed in claim 1, wherein said derivativeof phthalic acid diester is diethyl 4-methylphthalate, diethyl4-tert-butylphthalate, diethyl 4-bromophthalate, diethyl4,5-dichlorophthalate, di-n-butyl 4-chlorophthalate, di-n-butyl4,5-dichlorophthalate, diisohexyl 4-bromophthalate, di-n-butyl4-methylphthalate, di-n-butyl 4-tert-butylphthalate, diisobutyl4-methylphthalate, diisobutyl 4-tert-butylphthalate, dineopentyl4-methylphthalate, dineopentyl 4,5-dimethyl-phthalate, di-n-butyl4-bromophthalate, diisobutyl 4-bromophthalate, diisobutyl4,5-dichlorophthalate, dineopentyl 4-bromophthalate, dineopentyl3-fluorophthalate, dineopentyl 4-tert-butylphthalate, diisooctyl4-methylphthalate or diisooctyl 4-bromophthalate.
 9. A solid catalystfor polymerization of olefins which comprises: (A) a solid catalystcomponent for polymerization of olefins as claimed in claim 1; (B) anorganoaluminum compound of the following general formula (2): R⁴_(p)AlQ_(3−p)  (2) wherein R⁴ is an alkyl group of 1 to 4 carbon atoms;Q is a hydrogen atom or a halogen atom; and p is an integer of O<p≦3;and (C) an organosilicon compound of the following general formula (3):R⁵ _(q)Si(OR⁶)_(4−q)  (3) wherein R⁵ is the same or different,representing an alkyl group of 1 to 12 carbon atoms, a cycloalkyl group,a phenyl group, a vinyl group, an allyl group, or an aralkyl group; R⁶is the same or different, representing an alkyl group of 1 to 4 carbonatoms, a cycloalkyl group, a phenyl group, a vinyl group, an allylgroup, or an aralkyl group; and q is an integer of 0≦q≦3.
 10. A solidcatalyst component for polymerization of olefins, which comprises adialkoxymagnesium, (b) titanium tetrachloride, and (c) a phthalic aciddiester or a derivative thereof of the following general formula (1):

wherein R¹ is an alkyl group of 1 to 8 carbon atoms or a halogen atom;R² and R³ are the same or different, representing an alkyl group of 1 to12 carbon atoms; the number n of the substituent R¹ is 0, 1 or 2, andwhen n is 2, R¹ may be the same or different; provided that when n is 0,R² and R³ each is an alkyl group of 4 to 8 carbon atoms having atertiary carbon atom, and which is prepared by suspending saiddialkoxymagnesium in an aromatic hydrocarbon solvent which is liquid atordinary temperature, followed by contact with said component (c) andthen with said component (b), or by suspending said dialkoxymagnesium inan aromatic hydrocarbon solvent which is liquid at ordinary temperature,followed by contact with said component (b) and then with said component(c).
 11. A solid catalyst for polymerization of olefins which comprises:(A) a solid catalyst component for polymerization of olefins as claimedin claim 10; (B) an organoaluminum compound of the following generalformula (2): R⁴ _(p)AlQ_(3−p)  (2) wherein R⁴ is an alkyl group of 1 to4 carbon atoms; Q is a hydrogen atom or a halogen atom; and p is aninteger of 0<p≦3; and (C) an organosilicon compound of the followinggeneral formula (3): R⁵ _(q)Si(OR⁶)_(4−q)  (3) wherein R⁵ is the same ordifferent, representing an alkyl group of 1 to 12 carbon atoms, acycloalkyl group, a phenyl group, a vinyl group, an allyl group, or anaralkyl group; R⁶ is the same or different, representing an alkyl groupof 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, an vinylgroup, an allyl group, or an aralkyl group; and q is an integer of0≦q≦3.
 12. A solid catalyst component for polymerization of olefins asclaimed in claim 1, wherein the solid catalyst component is prepared bycontacting the component (a), the component (b), and the component (c)in the presence of an aromatic hydrocarbon compound which is in a liquidstate at ordinary temperature and has a boiling point at approximately90 to 150° C.
 13. A solid catalyst component for polymerization ofolefins as claimed in claim 1, wherein R¹ is an alkyl group of 1 to 8carbon atoms or a halogen atom; R² and R³ are the same or different,representing an alkyl group of 1 to 12 carbon atoms; the number n of thesubstituent R¹ is 1 or 2, and when n is 2, R¹ is a halogen atom.
 14. Asolid catalyst component for polymerization of olefins as claimed inclaim 10, wherein said phthalic acid diester is dineopentyl phthalate,tert-butyl neopentyl phthalate or bis(2,2-dimethylhexyl)phthalate.